Multistage thermolysis method for safe and efficient conversion of e-waste materials

ABSTRACT

Clean, safe and efficient methods, systems, and processes for utilizing thermolysis methods to processes to convert various e-waste sources into Clean Fuel Gas and Char source are disclosed. The invention processes e-waste sources, such as for example whole circuit boards, to effectively shred and/or grind the waste source, and then process using thermolysis methods to destroy and/or separate halogen and other dangerous components to provide a Clean Fuel Gas and Char source, along with the ability to recover precious metals and other valuable components from the Char.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119 to provisionalapplication Ser. No. 62/273,751 filed Dec. 31, 2015, titled MultistageThermolysis Method for Safe and Efficient Conversion of E-WasteMaterials, herein incorporated by reference in its entirety including,without limitation, the specification, claims, and abstract, as well asany figures, tables, or drawings thereof.

FIELD OF THE INVENTION

The invention relates to clean, safe and efficient methods, systems andprocesses for utilizing thermolysis methods to processes to convertvarious e-waste sources into a Clean Fuel Gas and Char source.Thermolysis provides an advanced pyrolysis methodology for heating andconverting e-waste sources as disclosed herein. In a particular aspect,the invention processes e-waste sources, such as, for example, wholecircuit boards, to effectively shred and/or grind the waste source, andthen process using thermolysis methods to separate, neutralize and/ordestroy halogen and other hazardous components to provide a Clean FuelGas and Char source, along with the ability to recover precious metalsand other valuable components from the Char.

BACKGROUND OF THE INVENTION

The global e-waste market creates over 50 million tons per year with anestimated 3% (1.5 million tons) in printed wiring boards (PWB), alsoreferred to as printed circuit boards (PCB) and an estimated 30% (15million tons) in plastic resins. The U.S. alone contributes betweenabout 28-33% of the global e-waste totals. The e-waste market isexpected to continue to increase an estimated 10-15% annually with theglobal consumer demand appetite for newest electrical and electronicequipment. Simply put, the world is awash in e-wastes. The result is acritical and worsening economic environment in need for solutions todiscarded e-waste products. Globally, the values of precious metals,copper and aluminum (predominant in e-waste sources) have fluctuatedsignificantly further reducing the interest in effectively recovering orrecycling components from the ever-growing e-waste recycling/recoverymarket. In addition, various state regulations aim to restrict or limitlandfill dumping of e-waste sources, resulting in significantly reducedincentives for processing e-waste sources.

Accumulating e-waste sources present a number of difficulties indeveloping processing techniques. Different approaches have been usedfor processing waste electrical and electronic equipment (WEEE), a termbroadly referring to the spectrum of products ranging from computers,printers and faxes, to washing machines. In particular, WEEE areclassified into 14 distinct categories including: Large householdappliances; Small household appliances; IT and telecommunicationsequipment; Consumer equipment; Lighting equipment; Electrical andelectronic tools; Toys, leisure and sports equipment; Medical devices;Monitoring and control instruments; Automatic dispensers; Displayequipment; Refrigeration equipment; Gas discharge lamps; andPhotovoltaic panels.

The four major categories of e-waste which are included in the WEEEclassifications include: Printed Wiring Boards (PWBs), e-plastics, Flatscreen displays (FSDs) and toner cartridges. As one skilled in the artascertains, myriad other types of electrical and electronic devices suchas cell phones, laptops, handhelds, appliances, and other devices areall included within these classifications. Electronics recycling ishistorically a very labor intense operation. This is a result of thediverse compositions making up e-waste sources. Plastic housings fromelectronic devices are ineffectively recycled as collection, sorting,re-pelletizing and shipping costs may be twice as high as the costs forvirgin raw materials based on natural gas-based feed stocks. FSDscontaining mercury provide another example of expense to process e-wastesources. Each flat screen display requires approximately 20 minutes'disassembly to remove the delicate mercury lamps. In addition to theultra-high costs associated with this recycling process, the frequentmercury contamination from poor disassembly processing and breakagepresent a huge issue to recyclers. These examples demonstrate that themanual recycling of e-waste sources does not provide a cost-effectivesolution to the accumulating e-waste supply.

There are also safety concerns with processing e-waste sources. Asignificant percentage of the recycled polymers contain toxic compounds,including halogenated hydrocarbons and organics, antimony oxides andother polymer additive flame and/or fire and/or fire retardants.Description of hazards of halogenated substances in electrical andelectronic equipment is described by Watson et al., Greenpeace ResearchLaboratories Technical Note, January 2010. These components areformulated in plastic housings and other components of e-waste sourcesto provide fire retardancy, as required to meet the global UL-94flammability regulations. As a result, the housings cannot easily belandfilled due to the toxic flame and/or fire retardants. In the U.S.the EPA will not allow smelters to process circuit boards and releasethese toxins into the environment. Such toxins result from thecombustion of halogenated hydrocarbons and organics generating toxicbyproducts such as aromatics and polycyclic aromatic hydrocarbons(PAHs), halogenated dibenzodioxins, halogenated dibenzofurans,biphenyls, pyrenes, and the like. Combustion processes generate thesetoxic materials which then must be removed downstream of the process andthereby render incineration approaches unsuccessful and/or noteconomical. As a result, large volumes of e-waste are shipped off-shoreto smelters, which are becoming less economically attractive due to hightransportation, processing and environmental costs. Moreover, thesmelting process is inefficient and a large percentage of metals can belost in the smelting process.

There remains a need for efficient processing of a variety of e-wastesources. A 2013 World Intellectual Property Organization (WIPO) patentlandscape report titled E-Waste Recycling Technologies identify a myriadof end products and components, including the following categories anddescriptions:

Batteries (containing hazardous cadmium and other toxins), PrintedWiring Boards and Wires or Cables.

Capacitors—components making up a large proportion of electronics on acircuit board and contain exotic and often hazardous materials used asdielectrics

LEDs—another common Printed Wiring Board sub-component and typically ina discrete package, these components also contain a mix of materialclasses, such as semiconductors, ferrous and non-ferrous metals andplastics.

Magnetic components—an interesting class in that these are likely aprimary source of rare earth elements, in particular neodymium.

Computers/laptops; Hand-held Devices; Displays; HouseholdAppliances—these topics are the primary “end product” types mentioned inthe WIPO landscape. The displays are somewhat of a hybrid source as theycan be both end products in television or computer monitor form, orcomponents, such as part of a mobile device, laptop or tablet device.

Telecom equipment—this grouping of e-waste is one of high priority.Driven by the subscriber business model and rapid obsolescence of themobile device industry, mobile phones, tablets and other devices make upa very large proportion of the e-waste streams in most countries. Inaddition to phones and tablets other telecommunications equipment isalso included, such as smartphones, switch gear, interconnect servers,mobile phones, stationary landline phone and hubs, for example.

Accordingly, it is an objective of the claimed invention to solve thelong-standing problem and need in the art for efficient methods forprocessing a myriad of e-waste sources.

A further object of the invention is to provide methods, systems, and/orprocesses for utilizing thermolysis methods to safely and efficientlyconvert various e-waste sources to a Clean Fuel Gas and Char sourcewithout generation (and further the removal of) toxic byproducts,including small molecules, including those chlorinated polymers commonlyused in these waste input streams. Toxic byproducts further include, forexample, VOCs, aromatics and polycyclic aromatic hydrocarbons (PAHs),dioxins and furans, including halogenated dibenzodioxins and halogenateddibenzofurans, biphenyls, pyrenes, cadmium, lead, antimony, arsenic,beryllium, chlorofluorocarbons (CFCs), mercury, nickel and other organiccompounds. As a result, the methods, systems, and/or processes of theinvention meet even the most rigid environmental standards.

A further object of the invention is to provide methods, systems, and/orprocesses for utilizing thermolysis methods to safely and efficientlyconvert various e-waste sources to a Clean Fuel Gas and Char source. Inparticular, the generation of a Clean Fuel Gas provides a desirablewaste-to-energy pathway from a previously unutilized waste sourcethrough the recycling of tars and oils to generate Clean Fuel Gas tothereby reuse the energy that went into the original fabrication. In afurther application, the generation of the Char source is suitable forfurther recycling and/or use of the Char source for further separationof desirable components for various applications as disclosed pursuantto the invention.

A further object of the invention is to utilize thermolysis methods todestroy (and beneficially not generate any additional) toxic halogenatedorganic compounds present in certain components of the waste sources.

A further object of the invention is to utilize thermolysis methods togenerate clean, usable fuel gas sources substantially-free or free ofhalogenated organic compounds (including VOCs).

A further object of the invention is to utilize thermolysis methods togenerate Char containing valuable electronic metals, precious metals,glass reinforcement and other materials, all of which aresubstantially-free or free of halogenated organic compounds (includingVOCs).

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

An advantage of the invention is the clean and efficient methods,systems, and/or processes for Thermolysis methods to safely andefficiently convert various e-waste sources to a Clean Fuel Gas and Charsource. It is a further advantage of the present invention that e-wastesources are converted by destroying toxic halogenated organic andhydrocarbon compounds present therein; clean, usable fuel gas sourcessubstantially-free or free of halogenated organic or hydrocarboncompounds are generated; and Char containing valuable electronic metals,precious metals, glass reinforcement and other materials, all of whichare substantially-free or free of halogenated or hydrocarbon organiccompounds, are further generated.

In an aspect of the invention, a method for converting an electricand/or electronic waste source to a Clean Fuel Gas and Char sourcecomprises: inputting an electric and electronic waste source into athermolysis system; undergoing a depolymerization and a crackingreaction of hydrocarbons in the waste source; destroying and/or removingtoxic compounds present in the waste sources; and generating the CleanFuel Gas and Char source. In a further aspect, the Clean Fuel Gas sourceis used for power to a system or application, the Char source containsrecoverable metals, and the Clean Fuel Gas and Char source aresubstantially-free of halogenated organic compounds.

In an aspect of the invention, a method for converting e-waste sourcesto a Clean Fuel Gas and Char source is provided and comprises: shreddingor grinding an e-waste source to provide a substantially uniform e-wastesource having an average diameter of less than 1 inch into a thermolysissystem comprising at least one reactor with a process temperature offrom about 300° C.-800° C. and a pressure range from about 10 to about100 millbar, wherein the system is provided indirect heat that is freeof oxygen; undergoing a depolymerization and a cracking of hydrocarbonsin the e-waste source; destroying and/or removing toxic compoundspresent in the e-waste sources; generating a Char, wherein the Char is afine metallic state that is free of halogenated organic compounds andcomprises valuable electronic metals, rare earth metals, preciousmetals, glass reinforcement and/or other materials; separating themetals, glass reinforcement and/or other materials from the Char; andgenerating a Clean Fuel Gas source from the pyrolytic conversion ofhydrocarbons in the e-waste source, wherein the fuel gas source is freeof halogenated organic compounds, and wherein from about 3,000 to 19,000BTUs per pound of e-waste source is generated as the fuel source; andproviding at least a portion of the fuel gas source to the method forconverting e-waste sources to provide an energy source for such method.

In a further aspect, products produced by the described processes andmethods for converting waste sources are provided.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing orphotograph executed in color. Copies of this patent or patentapplication publication with color drawing(s) will be provided by theOffice upon request and payment of the necessary fee.

FIG. 1 shows a process diagram for the methods, systems, and/orprocesses of the present invention.

FIG. 2 shows a depiction of e-waste (PWBs) suitable for processingaccording to the methods, systems, and/or processes of the presentinvention.

FIGS. 3-4 show photographs of e-waste input (PWBs) having been groundaccording to an initial processing step according to the methods,systems, and/or processes of the present invention. FIG. 3 shows e-wasteinput source in the form of ground e-plastics. FIG. 4 shows e-wasteinput source in the form of ground printer cartridges.

FIGS. 5-6 show photographs of e-waste inputs, including whole plasticmaterial (FIGS. 5A, 5B, 5C), including multiple types of large e-plasticwaste inputs (FIG. 5A), a plastic computer monitor enclose (FIG. 5B),and miscellaneous e-plastic printer enclosures (FIG. 5C), and mixedplastic material (FIGS. 6A, 6B, 6C), including a plastic part noting itis made from ABS (acrylonitrile butadiene styrene) plastic (FIG. 6A),plastic part noting it is made from ABS-FR (fire retardant) plastic(FIG. 6B), and plastic part noting it is made from PC (polycarbonate)plus ABS with FR plastic (FIG. 6C), each for processing according to themethods, systems, and/or processes of the present invention.

FIG. 7 shows a photograph of the whole plastic material having beenground according to an initial processing step according to the methods,systems, and/or processes of the present invention.

FIGS. 8-9 show photographs of Char generated from the e-waste inputaccording to the methods, systems, and/or processes of the presentinvention.

FIGS. 10-15 show photographs of separated materials in phases ofseparation according to optional embodiments of the invention from cleanChar including: Oversized copper materials (1.3+ mm) (FIG. 10), Smallersized copper and precious metal materials (FIG. 11), additional finersized copper and precious metal materials (FIG. 12), <300 um sizedcopper and precious metal materials (FIG. 13), additional finer sizedcopper and precious metal materials (FIG. 14), and primarily fine carbonmaterial (FIG. 15).

FIG. 16 depicts representative temperature measurements in the reactorsemployed for processing e-waste inputs according to embodiments of theinvention.

FIG. 17 depict representative gas flow measurements in the reactorsemployed for processing e-waste inputs according to embodiments of theinvention.

FIG. 18 depicts representative temperature measurements in the reactorsemployed for processing e-waste inputs according to embodiments of theinvention.

FIG. 19 depict representative gas flow measurements in the reactorsemployed for processing e-waste inputs according to embodiments of theinvention.

Various embodiments of the present invention are described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The embodiments of this invention are not limited to particular methods,systems, and/or processes for thermolysis methods to safely andefficiently convert various e-waste sources, which can vary and areunderstood by skilled artisans. It is further to be understood that allterminology used herein is for the purpose of describing particularembodiments only, and is not intended to be limiting in any manner orscope. For example, as used in this specification and the appendedclaims, the singular forms “a,” “an” and “the” can include pluralreferents unless the content clearly indicates otherwise. Further, allunits, prefixes, and symbols may be denoted in its SI accepted form.Numeric ranges recited within the specification are inclusive of thenumbers defining the range and include each integer within the definedrange.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which embodiments of the invention pertain. Many methods andmaterials similar, modified, or equivalent to those described herein canbe used in the practice of the embodiments of the present inventionwithout undue experimentation, the preferred materials and methods aredescribed herein. In describing and claiming the embodiments of thepresent invention, the following terminology will be used in accordancewith the definitions set out below.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “substantially-free,” as used herein may refer to a minimalamount of a non-desirable and/or toxic component in a material, such asa Char generated by the methods, processes and systems of the invention.In an aspect, a material is substantially-free of a defined component ifit contains less than a detectable amount of the defined component, orless than about 10 parts per billion (ppb), or more preferably less thanabout 1 ppb. In an embodiment, Char and fuel gas generated according tothe processing of e-waste is substantially-free of toxins, includinghalogens, having less than about the detection limit of about 10 ppb, ormore preferably less than about 1 ppb of the toxin, including halogens.For toxic and/or hazardous materials, free represents an amount belowthe detection limit of the appropriate material within experimentalerror. In an aspect of the invention the Char and fuel gas generatedaccording to the processing of e-waste is free of toxins, indicatingthat there is a non-detectable amount of toxins in the measured source.

The term “substantially-free,” as used herein referring to oxygen in thethermolysis methods refers to a minimal amount of oxygen or air. In anaspect, a system is substantially-free of oxygen if it contains lessthan about 4 wt.-%, and preferably less than about 2 wt.-%.

The term “thermolysis” as used herein is generally referred to as athermal-chemical decomposition conversion process employing heat to aninput source in need of conversion to a Clean Fuel Gas and Char source.Thermolysis refers generally to thermal-chemical decomposition oforganic materials at temperatures >300° C. and in some instances in theabsence of external oxygen to form gases, tars, and oils and Chars thatcan be used as chemical feedstocks or fuels. Tars and oils representgroups of volatile organic compounds, viscous liquids, paraffins, waxes,aromatics, aliphatics, fats and other petrochemical based organicmixtures for example. The thermolysis methods disclosed according to thepresent invention are an advancement over conventional pyrolysis and/orthermolysis methods, which employ fire or a heat source and include anoil as an output. As described herein according to the invention no oilis generated as an output of the thermolysis methods of the presentinvention. As disclosed in further detail herein, the presentthermolysis methods employ at least a reprocessing of any tars and oils.Based on at least these distinctions between the thermal conversionmethods, the terms thermolysis and pyrolysis are not synonymous, asthermolysis provides various beneficial improvements not previouslyachieved by pyrolysis methods and/or conventional thermolysis methods.

The term “weight percent,” “wt.-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt.-%,” etc.

The methods, systems, and/or compositions of the present invention maycomprise, consist essentially of, or consist of the components andingredients of the present invention as well as other ingredientsdescribed herein. As used herein, “consisting essentially of” means thatthe methods, systems, and/or compositions may include additional steps,components or ingredients, but only if the additional steps, componentsor ingredients do not materially alter the basic and novelcharacteristics of the claimed methods, processes and/or systems.

It should also be noted that, as used in this specification and theappended claims, the term “configured” describes a system, apparatus, orother structure that is constructed or configured to perform aparticular task or adopt a particular configuration. The term“configured” can be used interchangeably with other similar phrases suchas arranged and configured, constructed and arranged, adapted andconfigured, adapted, constructed, manufactured and arranged, and thelike.

The methods, systems, and/or processes of the present invention relateto thermolysis methods to safely and efficiently convert various e-wastesources to a Clean Fuel Gas and Char source. Beneficially, the methods,systems, and/or processes of the present invention provide significantand unexpected advances beyond conventional thermolysis methods. Forexample, conventional combustion processes which burn e-waste sourcesare highly unpredictable and difficult to control. Although advancementsin thermolysis have been made in the prior art, the present inventionbeneficially exceeds the capabilities of known thermolysis methods inconverting e-waste sources into valuable outputs which beneficiallydestroy (and do not generate any new) toxic halogenated organiccompounds present in e-waste sources. Moreover, the thermolysis methodsof the invention include the use of multiple reactors, reinjection andcracking of any and all tars and oils that are created. As a furtherbenefit, the methods, systems, and/or processes of the present inventiongenerate clean, usable fuel gas sources substantially-free or free ofhalogenated organic compounds. As a still further benefit, the methods,systems, and/or processes of the present invention generate Charcontaining valuable electronic metals, precious metals, glassreinforcement and other materials, all of which are substantially-freeor free of halogenated organic compounds. Notably, the methods, systems,and/or processes of the present invention do not simply reduce theamounts of brominated compounds and other toxins, instead these areremoved (with no additional generation) from the treated e-waste sourceswhile further providing the useful and valuable outputs of the inventiondefined further herein.

E-Waste Sources

The methods, systems, and/or processes of the present invention relateto of novel process using thermolysis methods too safely and efficientlyconvert various electrical and electronic equipment (WEEE), includinge-waste sources. As referred to herein, “e-waste” sources include, butare not limited to: (i) printed wiring boards (PWB), includingelectronic circuit boards (ECBs), including the electronic componentsand wiring attached to the PWB, as well as glass fibers held togetherwith epoxies that contain brominated flame and/or fire retardants (FR),(ii) the e-plastic materials employed along with the PWB, includeplastic housings, cases, bases, supports, frames, enclosure, terminalsconnectors and other polymeric parts, (iii) flat panel displays (FPDs),including steel, e-plastics, aluminum, glass, PWBs and mercury lampscontained therein, and (iv) printer cartridges and/or cassettes, tonercartridges, solvents, and ink-containing modules.

As one skilled in the art will ascertain, e-waste sources according tothe invention differ based upon factors including the polymer type,flame and/or fire retardancy of the e-waste source, namely thehalogenated flame and/or fire retardants for thermoplastic polymersdesigned for a particular polymer system employed in the e-waste source.Halogenated flame and/or fire retardants were engineered to matchcompatibility with a specific polymer system and to meet designedUnderwriters Laboratories of the USA (UL) requirements, agency andindustry test standards. As a result, there are significant differencesamong flame and/or fire retardant polymeric materials contained ine-waste sources requiring processing according to this invention. Themethods, systems, and/or processes of the present invention unexpectedlyprovide suitable conditions for the conversion of such diverse e-wastesources into desirable outputs. However, the nature of the e-wastesource will impact that particular thermolysis methods, systems, and/orprocesses of the present invention to convert such e-waste source into aClean Fuel Gas and Char source.

Without being limited to a particular theory of the invention, additiveflame and/or fire retardants are generally formulated for thermoplasticpolymers (such as those used in plastic housings and/or cabinetry forelectronics, including those plastics containing PWB) are unique fromreactive flame and/or fire retardants used in an epoxy backbone of aPWB. Beneficially, the Thermolysis method is suited for processing bothtypes of e-waste sources with modifications to the processing methods,systems and/or apparatuses disclosed herein.

PWB and ECBs Containing Reactive Flame and/or Fire Retardant Polymers inEpoxy Backbones (FR4) as an E-Waste Source

In an aspect of the invention, PWBs, including ECBs, are a suitablee-waste source for use according to the methods, systems, and/orprocesses of the present invention. PWBs contain precious metals,organics, hazardous halogenated flame and/or fire retardants (alsoreferred to as flame and/or fire retardant polymers), and fiberglass.ECBs are an e-waste source which include the electronic components andwiring attached to the PWB, such as glass fibers or fabric held togetherwith epoxies that also contain halogenated flame and/or fire retardants.The use of the term PWBs employed herein this description are furtherunderstood to include the ECBs.

In an aspect, PWBs processed according to the invention enables themetals in PWBs to be recovered by refining (instead of smelting) orchemical or electrochemical separation for individual metals, andfurther recovers fiberglass, each of which has the further benefit ofeliminating any toxic components (such as dioxins and furans) from thegenerated Char containing the metals. Moreover, the refining and removalof fiberglass further reduces the amount of Char that contains theprecious metals. Beneficially, the metals are recovered substantially intheir original form and most have not been melted, which preserves thevalue of the metals. In an aspect of the invention, at least 50%recovery of the metals, including precious metals (e.g. gold, silver,palladium), electronic metals (e.g. copper, aluminum), and rare earthmetals are recovered from the Char through separation methods,preferably at least about 55%, preferably at least about 60%, preferablyat least about 65%, preferably at least about 70%, preferably at leastabout 75%, preferably at least about 80%, preferably at least about 85%,preferably at least about 90%, or most preferably at least about 95%. Asreferred to herein, “separation” means the division of the content ormatter—in this case the metals in the char—into constituent or distinctelements such as gold, palladium etc. These and other benefits ofprocessing PWB e-waste sources according to the invention are disclosedhere.

In an aspect of the invention, reactive flame and/or fire retardantpolymers used in an epoxy backbone of a PWB are a suitable e-wastesource for use according to the methods, systems, and/or processes ofthe present invention. As referred to herein, an epoxy is a crosslinkedmatrix where the flame and/or fire retardant groups are locked in thepolymer matrix, such that the halogenated group (such as bromine)thermally stabilizes the epoxy polymer during high heat operations, thependant halogenated group (such as Br-groups) protect epoxide linkagesfrom chemical, moisture and oxidation during PWB service life, and thehalogenated group (such as bromine) is released only with direct openflame and/or fire or hot wire exposure (such as from shorted surfacemount devices). E-waste sources employing reactive flame and/or fireretardant polymers in an epoxy backbone of a PWB generally do not useantimony (Sb) or any other specific synergist for electrical reasons.

Circuit boards containing an FR4 epoxy board with attached electronicdevices and components are a commonly found e-waste source. As anexample, brominated epoxy resins are used for FR4 laminates used ascircuit boards (PWB), encapsulation compounds for coating devices andcircuit components, and sealants or putties to protect electronicdevices on boards or within the electronic housings. In this e-wastesource, tetrabromobisphenol A (TBBPA), the bromine containing moleculeas shown by the following formula for tetrabromo BPA-epoxide, for epoxy,also may be found in polybutylene terephthalate (PBT), nylon andurethanes as found in e-waste sources according to embodiments of theinvention:

is reacted into the epoxy polymer backbone forming a polymer. Thebromine atoms from the TBBPA protect the epoxy chemical linkages fromchemicals used in board processing, increase thermal resistanceproperties of the material, hydrolytic stability and resistance to moistenvironments and provide flame and/or fire spread protection fromsurface wires and mounted devices. TBBPA, as an exemplary FR4 PWBlaminate e-waste source contains from about 16-20% bromine (ULrequirements for flammability and hot wire ignition testing). FR4laminates contain 40-60% woven glass matt, resulting in bromine contentof 8-12% in the FR4 laminate. This bromine content in the form ofbromine atoms on the TBBPA molecule are released when exposed to adirect flame and/or fire situation to extinguish the flame and/or firesource (such as associated with short circuits or overloads on thecircuit board). As a skilled artisan will ascertain, the bond energymaintains the bromine atom and the epoxy resin stable during elevatedoperating conditions (such as solder bath processing or other boardprocessing processes) without releasing the corrosive bromine ions. ULrequirements call for applications that have a direct 110-220 voltelectrical connection for either continuous operation or chargingoperations to classify as flame and/or fire retarded. Similarly, thelaminate must be UL bulletin 94 V-0 to classify as self-extinguishing

As of result of these characteristics of the flame and/or fire retardantpolymers, including for example FR4 laminates, there is a benefit toprocessing the flame and/or fire retardant polymers used in an epoxybackbone of a PWB as a single e-waste source according to someembodiments of the invention.

Thermoplastic Housings as an E-Waste Source

In an aspect of the invention, e-plastics or thermoplastics are asuitable e-waste source for use according to the methods, systems,and/or processes of the present invention. The volume of E-plastics orthermoplastics many of which contain hazardous flame and/or fireretardants is approximately ten times the volume of PWBs as a result ofa wide variety of plastics employed. In an aspect, e-plastics orthermoplastics processed according to the invention recovers the energyin the plastics and returns it as a reusable energy source, and furthersafely decomposes hazardous flame and/or fire retardants without theproduction of any toxic components (such as dioxins and furans). Theseand other benefits of processing PWB e-waste sources according to theinvention are disclosed here.

In an aspect of the invention, thermoplastic housings many of whichcontain flame and/or fire retardant polymers used in plastic housingsand/or cabinetry for electronics are a suitable e-waste source for useaccording to the methods, systems, and/or processes of the presentinvention. Without being limited to a particular type of e-wasteprocessed and recycled according to the invention, it is estimated thatglobally for every ton of PWB there will be approximately 10 tons of thethermoplastics housing the PWB in need of processing. Accordingly,thermoplastic housings represent a significant e-waste source in need ofprocessing according to the embodiments of the invention.

As referred to herein, flame and/or fire retardant polymers used inhousings are an additive halogenated molecule (such as bromine orchlorine) chemically designed to blend with the plastic polymers duringcompounding. Such flame and/or fire retardant molecules migrate withinthe polymer matrix during thermal exposure or flame and/or firecombustion. Further the flame and/or fire retardant molecules arecompounded with antimony trioxide (Sb₂O₃) as a powerful synergistresulting in antimony tribromide (SbBr₃) designed to smother a flameand/or fire and form insulating Char on the surface. Overall, such flameand/or fire retardant polymers used in e-waste housings have aplasticizing effect which are known to dilute the physical properties ofthe polymer instead of improve.

Thermoplastic housings, enclosures, cases and other modules containingflame and/or fire retardant polymers are an abundant e-waste source. Forexample, brominated flame and/or fire retardants for thermoplasticpolymers are chemically designed for each base polymer system. Theadditive flame and/or fire retardant (FR) molecules are added during theresin compounding process along with other additives, colorants,stabilizers and reinforcements. Exemplary polymers and theirapplications include: FR-acrylonitrile butadiene styrene (ABS) suitablefor high gloss external housings, covers, bezels and doors;Polycarbonates suitable for housings that require physical strength,durability and toughness with desirable appearance; FR-HIPS (High ImpactPolystyrene) suitable for housings, covers, enclosure with low endeconomics and low physical property requirements; FR-Polypropylenesuitable for low cost electronic covers or cases that require lowersurface appearance; PVC suitable for low cost electronic covers, doors,and housings that have low physical property requirements and low costpressures; FR-Nylon & PBT suitable for electrical connectors, terminals,wire blocks, sockets, etc. The design of these and other flame and/orfire retardants for thermoplastic housing polymers is focused on notcompromising the physical properties of the base polymer while migratingto the surface of the polymer during thermal exposure to be available tocombine with antimony trioxide (Sb₂O₃) at the critical point of flameand/or fire exposure or ignition point. These halogenated flame and/orfire retardants are compounded with antimony trioxide (Sb₂O₃) which actsas a synergist to form the heavy gas antimony tribromide (SbBr3) tochoke the open flame and/or fire and cool the combustion site to stopthe flame and/or fire propagation.

As of result of these characteristics of the flame and/or fire retardantthermopolymers, there is a benefit to processing the flame and/or fireretardant polymers used in plastic housings, enclosures, cases,cabinetry, and other modules for electronics as a single e-waste sourceaccording to some embodiments of the invention.

Flat Panel Displays as an E-Waste Source

In an aspect of the invention, flat panel displays (FPDs) are a suitablee-waste source for use according to the methods, systems, and/orprocesses of the present invention. FPDs as an e-waste source includevarious components such as steel, plastic, aluminum, glass, boards andhazardous mercury lamps contained therein. In an aspect, FPDs processedaccording to the invention safely extracts and eliminates mercury andhazardous flame and/or fire retardants without the production of anytoxic components (such as dioxins and furans). These and other benefitsof processing FPD e-waste sources according to the invention aredisclosed here.

In an aspect, the handling of mercury lamps contained within FPDsaccording to the methods of the invention do not require thetime-consuming and potentially hazardous step of an initial removal orseparation of a mercury lamp from within the FPDs. This is a significantbenefit as an FSD may contain up to 20 or more glass ampules eachcontaining 1-20 mg of mercury and sealed with as many as 60-70 screwswithin the FPD enclosure to protect the mercury ampules. This results ina time consuming process for the work to disassemble under HAZMATconditions. Instead, employing the methods, systems, and/or processes ofthe present invention obviates the need for the step and insteadprocesses the e-waste source within the closed, oxygen-free systemcapable of removing toxins, including mercury. Without being limited toa particular mechanism of action, the thermolysis methods beneficiallyvaporize any mercury and reacts with halogens in the scrubbers to frommercury halides, which can be safely removed from the internal wastewater treatment system.

Printer Cartridges and Cassettes as an E-Waste Source

In an aspect of the invention, printer cassettes and/or ink cartridgesare a suitable e-waste source for use according to the methods, systems,and/or processes of the present invention. Such printer cassettes and/orink cartridges include thermoplastics, solvent and carbon black/ink. Insome cases, these thermoplastics also include halogenated flame and/orfire retardants. Beneficially, the solvent provides a high level ofconversion potential and carbon black in the ink may further berecovered and re-used.

Combinations of e-Waste Sources

In an aspect of the invention, a combination of any of theaforementioned electrical and electronic equipment, including e-wastesources, may be processed in a combined processing according toembodiments of the invention.

Thermolysis Methods

The methods, systems, and/or processes of the present invention relateto thermolysis methods to safely and efficiently convert various e-wastesources to gas/vapor mixtures and carbonaceous materials, namely a CleanFuel Gas source and a Char that contains various metals, precious andotherwise. In an aspect, the gas/vapor including halogens are cleanedand removed as disposable salts. In a further aspect, any mercury isvaporized in the reactors of the system. The metals are recoveredsubstantially in their original form and most have not been melted. As aresult of the methods described herein, a clean Char source and fueledgas are the only products of the system.

As referred to herein the thermolysis methods employ a continuous,oxygen-free thermal process of e-waste sources using heat energy.Beneficially, the methods, systems, and/or processes of the presentinvention convert the e-waste sources by destroying and not generatingadditional toxic halogenated organic compounds present in e-wastesources. As a further benefit, the methods, systems, and/or processes ofthe present invention generate clean, usable fuel gas sourcessubstantially-free or free of halogenated organic compounds. As a stillfurther benefit, the methods, systems, and/or processes of the presentinvention generate a Char containing valuable electronic metals,precious metals, glass reinforcement and other materials, all of whichare substantially-free or free of halogenated organic compounds. In anaspect of the invention, at least 50% recovery of the metals, includingprecious metals (e.g. gold, silver, palladium), electronic metals (e.g.copper, aluminum), and rare earth metals are recovered from the Charthrough separation methods, preferably at least about 55%, preferably atleast about 60%, preferably at least about 65%, preferably at leastabout 70%, preferably at least about 75%, preferably at least about 80%,preferably at least about 85%, preferably at least about 90%, or mostpreferably at least about 95%. As a still further benefit, the inventionproviding for the generation of a Clean Fuel Gas and Char without theformation of (along with the destruction of) halogenated compoundsbeneficially prolongs the life span of the systems employed for thethermolysis methods. Without being limited according to a particularmechanism, the reduction of formation of halogenated compounds, such ashydrogen bromide which is known to form hydrobromic acid in solutionwith water, reduces the corrosive damage caused to the systems, such asvalves, filters, reactors and the like.

In an aspect the systems and apparatuses utilized for the methods andprocesses of the present invention includes at least the followingcomponents as substantially depicted in FIG. 1, including: a feedstockinput, airlock, at least one reactor (and preferably a series ofreactors), gas scrubbers, tar/oil crackers (or may be referred to ascracking reactor), collection tanks for Char, and output for Clean FuelGas. Additional optional components may include for example, a carbonremoval unit for removal of carbon from the Char. Modifications to thesesystems and apparatuses, including as described herein, are consideredwithin the level of ordinary skill in the art based upon the descriptionof the invention set forth herein.

In an aspect the methods, systems, and/or processes of the presentinvention include the steps as substantially depicted in FIG. 1,including the following processing steps: shredding, chopping and/orgrinding of the e-waste input; a reaction or series of thermolysisreactions in a substantially oxygen-free continuous, low pressurethermolysis process with indirect heating; employing more than onereactor for the thermolysis reactions; separation of Char; a tar and oilreprocessing or cracking step; and scrubbing of the fuel gas.

The methods, systems, and/or processes of the present invention mayoptionally include one or more of the following steps: separation ofe-waste sources; drying the e-waste input, removing any valuablecomponents from an e-waste source; extraction of metals or othercomponents from the ground and/or shredded e-waste input; separationstep and additional gas scrubbers; collection and separation ofcomponents from the Char (e.g. carbon, metals).

The methods, systems, and/or processes of the present invention can becarried out in a variety of apparatus for thermolysis. An exemplarydevice or series of reactors, further including oil and otherseparators, char/oil separators, gas scrubbers, evaporators, and thelike are shown for example in U.S. Patent Publication No. 2014/0182194,which is incorporated herein by reference in its entirety.

In an aspect the invention includes an initial optional step ofseparating e-waste sources for processing according to the invention. Inan aspect, one or more types of e-waste may be separated for independentprocessing according to the methods of the invention. For example, PWBsmay be removed from the thermoplastic housings containing the PWBs andseparated as e-waste input sources for processing thereafter. In anembodiment, the separated e-waste input sources can be processed usingseparate reactor systems or may be processed using the same reactorsystems in different batches. As shown in FIG. 2, various e-wastesources (as depicted PWB) may be processed according to an embodiment ofthe invention. As shown in FIG. 3, various e-waste sources (as depictede-plastics) may be processed according to an embodiment of theinvention. As shown in FIG. 4, various e-waste sources (as depictedprinter cartridges) may be processed according to an embodiment of theinvention. As shown in FIGS. 5-7, various e-waste sources (as depictedplastic materials, including whole plastic and mixed plastic) may beprocessed according to an embodiment of the invention.

In an aspect the invention includes an initial optional step of removingany valuable components prior to a shredding and/or grinding phase. Forexample, in an aspect, circuit boards may be removed from plasticmaterials (such as keyboards, laptops, iPhones/iPads, etc.) prior to theshredding and/or grinding of the e-waste source.

In an aspect, the invention includes an initial shredding, choppingand/or grinding step of the e-waste source, each of which may bereferred to herein as shredding and/or grinding. The scope of theinvention is not limited with respect to this initial processing step toreduce the size of the e-waste and provide a substantially uniform inputsource. In an aspect, the e-waste source can be placed directly into agrinder or shredder. In an aspect, the grinding and/or shredding stepprovides substantially uniform pieces of the input source. In an aspect,the grinding and/or shredding step provides pieces of the input sourcehaving an average diameter of less than about 2 inches, preferably lessthan about 1 inch (as shown in FIGS. 3-4 and 7), or in some aspects, toless than about 0.5 inches. In an aspect, the shredding and/or grindingcan include a first coarse step followed by a fine shredding and/orgrinding step. In an alternative aspect, the shredding and/or grindingcan include a single processing step.

Various shredding and/or grinding techniques may be employed accordingto the invention to provide the e-waste input source in a desirable sizeor form for processing. In a preferred aspect, the e-waste source, suchas a PWB, is ground and/or shredded to a size of less than about 1 inchto provide a substantially uniform input source. In a further preferredaspect, the substantially uniform input source is combined with any dustor other debris from the shredding and/or grinding step that isrecovered for processing according to the methods of the invention.

Beneficially, according to the invention a variety of e-waste sourcescan be processed according to the invention without substantialextraction steps to remove or separate various components for distinctand separate processing. This is a significant benefit over processingsystems and techniques of the prior art requiring substantial sortingand separation of components. As set forth in the 2013 WIPO reporttitled E-Waste Recycling Technologies, “the general intent at each stepis that complex materials should be sorted and separated as much aspossible into similar types of materials, e.g., steel with steel,aluminum with aluminum, copper with copper, etc. At each step a moreconcentrated output material becomes a more valuable input into anotherprocess, until a material is ready for the market as a new material.”The present invention does not require such extensive separation intosimilar types of materials for the processing of e-waste sources.

In an aspect, the invention includes an optional extraction step for theremoval of certain metals from the ground and/or shredded e-waste sourceinput. In an aspect, a step for extraction of metals immediately followsthe shredding and/or grinding of the e-waste source. As referred to inthis step, the extraction of metals includes ferrous metals andnon-ferrous metals (e.g. aluminum).

The removal step may include any techniques known to those skilled inthe art to which the invention pertains, including a combination ofmechanical and/or manual removal. In an aspect, the separation mayinclude the use of magnet separators, including magnetic and highmagnetism separators, for the attraction and removal of ferrous metals.

In a further aspect, the use of eddy current can be used to removemetals, such as copper and aluminum. In an aspect, the separation mayinclude the use of electrostatic separation. In an aspect, theseparation may include the use of specific gravity separation. In anaspect, the separation may include the use of an air or fluid sortingdevice

In an aspect, the invention involves a reaction or series of thermolysismethods and reactions in a substantially oxygen-free continuous, lowpressure, thermolysis process using heat energy. In an aspect, lowpressure includes from about 10 to about 100 millibar, or any rangetherein. In an aspect, the invention involves an oxygen-free continuous,low pressure, thermolysis process in a reactor or series of reactors. Asreferred to herein, the oxygen-free process in the reactor(s) does notinclude air or oxygen in contact with the e-waste input source.Beneficially, as a result of the reduction and/or elimination of oxygenfrom the methods, systems, and/or processes of the present invention,the e-waste input sources are not exposed to flame and/or fires orplasma source and therefore do not form polycyclic aromatic hydrocarbons(PAHs), halogenated dibenzodioxins, halogenated dibenzofurans,biphenyls, and/or pyrenes, or other halogenated organics In an aspect,the total aggregate composition of the e-waste sources comprising up to10% halogen content are processed according to the methods, systems,and/or processes of the present invention without the creation of PAHs,halogenated dibenzodioxins, halogenated dibenzofurans, biphenyls, and/orpyrenes.

In a further aspect, the invention further includes the destruction oftoxins, namely halogen compounds in addition to not generating anytoxins as mentioned above. In an aspect, the methods destroy aliphatics,aromatics, and polycyclic aromatic hydrocarbons, halogenateddibenzodioxins, halogenated dibenzofurans, biphenyls, pyrenes,chlorofluorocarbons, etc. Metals such as cadmium, lead, antimony,arsenic, beryllium, mercury, nickel and other organic compounds presentin the e-waste source are recovered essentially in their original state.

In an aspect, the invention employs the substantially oxygen-free oroxygen-free continuous, low pressure thermolysis process with supply ofheat energy. Thermolysis methods are known to employ different methodsand amounts of heat energy, including for example: Low temperaturethermolysis with a process temperature below 500° C.; medium-temperaturethermolysis in the temperature range 500 to 800° C.; and meltingthermolysis at temperatures of 800 to 1,500° C. According to aspects ofthe present invention, the substantially oxygen-free or oxygen-freecontinuous, low pressure thermolysis process applies indirect heating.In an aspect, the heating includes processing the e-waste source inputat temperatures of about 400° C.-800° C. Beneficially, the use of alower temperature thermolysis process places less stress on a reactor(s)(such as steel reactors), requires less energy to run the continuousprocess according to the invention, and further maintains metals incontact with the system at lower temperature ranges which improveslongevity, processing, etc. within a plant facility.

In an aspect, a reactor or series of reactors (also referred to ascascading reactors) allows for the thermolysis processing over the lowerrange of temperatures from about 400° C. to about 800° C. As one skilledin the art understands, there is not a single processing temperature foran input source according to the invention; instead a range oftemperatures within a reactor (or series of reactors) is obtained. Forexample, within a single reactor the input source within the head of thereactor may be at a higher temperature than the bottom of the reactor.In addition, as one skilled in the art understands, the use of a singlereactor may necessitate a higher temperature range, such as from about600° C. to about 800° C., whereas a series of reactors enables a lowerrange of temperatures, such as from about 400° C. to about 600° C. Inpreferred aspects, the reactor(s) employed according to the methods ofthe invention do not require design for withstanding hightemperature/pressure, as the relatively low temperature and pressuresare employed (such as on average about 650° C. and ambient pressures ofon average about 50 mbar).

The continuous thermolysis process is carried out in at least onereactor to undergo at least partial gasification. Various reactors knownin the art can be employed, including for example, rotary drum reactors,shaft reactors, horizontal reactors, entrained-flow gasifiers, fixed-bedgasifiers, entrained-flow gasifiers, or the like. Exemplary reactors aredisclosed, for example in, U.S. Publication No. 2014/0182194 and DE 10047 787, DE 100 33 453, DE 100 65 921, DE 200 01 920 and DE 100 18 201,which are herein incorporated by reference in its entirety. As oneskilled in the art will ascertain the number, sequence and scale of thereactors employed according to the invention can be adapted pursuant tothe scale and volume of e-waste sources inputted, which are embodiedwithin the scope of the invention.

In some embodiments, a primary reactor employed according to theinvention may comprise, consist of or consist essentially of inputregion with distributor, reactor mixing chamber, high-temperatureregion, high-temperature chamber, heating jacket chamber with burners,conversion section, inner register, and/or heat transfer register. Inexemplary embodiments, a secondary (or tertiary) reactor employedaccording to the invention may comprise, consist of or consistessentially of gas compartment with dome, high-temperature chamber withvertical conveying device, inner register and outer register, conversionsection with conveyor device, heating jacket chamber and/or combustionchamber.

In an aspect, the reactor(s) are jacket-heated. In an aspect, thereactors are vertically and/or horizontally disposed. In an aspect, atleast two reactors are employed. In an aspect, at least three reactorsare employed. In an aspect, the reactor(s) may optionally undergoagitation. In a preferred aspect, at least one reactor or a primaryreactor is vertical with a moving bed design and counter-current flowfor the fuel gas along the heated walls into secondary reactors. Withoutbeing limited according to an embodiment of the invention, such designsminimize the creation of undesirable tars and fuel oils. In a furtherpreferred embodiment, a moving bed design is further employed for asecondary horizontal reactor which extends the controlled reaction timeand temperature of the fuel gas and char from improved solid/gas andgas/gas reactions according to the invention.

The e-waste sources undergo the conversion in the reactor(s) for anamount of time sufficient to provide at least partial conversion andsubstantially as set forth according to the methods of U.S. PublicationNo. 2014/0182194. In an aspect, the amount of retention time in areactor(s) varies from at least about 20 minutes, at least about 30minutes, at least about 40 minutes, at least about 50 minutes, or atleast about 60 minutes as may vary based upon factors including forexample the shredded size of the input source which impacts thegasification reaction, and the like.

In an aspect, the pressure in the reactor(s) is held constant within apressure range from about 10 to about 100 millibar, or preferably fromabout 20 to about 50 millibar.

In an aspect, the methods further include a tar and oil cracking step.As one skilled in the art appreciates, tars and oils are an unavoidableproduct of the pyrolysis process, which are a non-heterogenous mixtureof olefins and parrafins, which contain tars and hazardous component.These hazardous components include carcinogenic benzene, toluene andchlorinated-brominated components, if PVC and/or flame retardants arepresent in the plastics feedstock. The pyrolytic oils have a low flashpoint and are known to be extremely hazardous (often requiring hazardousregulatory permits in various countries). Beneficially, according to theinvention such unavoidably created tars and oils are merely anintermediate and are subsequently cracked. As referred to herein,“cracking” refers to the process whereby complex organic molecules arebroken down into simpler molecules, such as light hydrocarbons, by thebreaking of carbon-carbon bonds in the precursors. Thus crackingdescribes any type of splitting of molecules under the influence ofheat, catalysts and solvents. Accordingly, tars and oils are notcollected or an output of the thermolysis methods of the invention. Inan aspect, a further gas converter (cracking reactor) will be employed,such as where higher organic components are further degraded. Thisremoval and conversion of these heavy oils or tars into Clean Fuel Gasis desired to remove these materials which selectively absorbhalogenated hazardous substances. In an aspect, the step recycles tarsand oils in order to remove the hazardous halogenated compounds. In afurther aspect, the tar and oil cracking step has the beneficial effectof creating more clean fuel gas.

In an aspect, the generated tars and oils are processed in the presenceof an optional catalyst, such as for example zeolite. In an embodiment,the cracking step separates light and heavy oils, such as disclosed forexample in U.S. Patent Publication No. 2014/0182194, which isincorporated herein by reference in its entirety.

In an aspect, the methods may further include an optional cooling stepfor the gas. In some embodiments, the gas will be cooled due to furtherprocessing in a scrubbing stage. For example, a cooled conversionchamber may be in connection with a reactor according to the methods ofthe invention. In an aspect, a gas at a temperature from about 400°C.-800° C. is cooled to a temperature below about 100° C., or preferablybelow about 80° C. The gas may further thereafter be cooled to anambient temperature, such as in an adjacent water scrubber to remove anyexcess water and/or steam from the gas.

In an aspect, the methods may further include a conditioning step, suchas employing and additional gas scrubbers. In an embodiment, gasproduced may be further purified following cooling at a gas scrubbingstage, i.e an alkaline stage (for example, NaOH for the binding of HCland HBr) and fed to the downstream process.

In an aspect, the invention further includes a cleaning step for thefurther processing when mercury-containing compounds were included inthe processed e-waste source. Elemental mercury will be removed in thewater scrubber. Such step may also include the removal of mercury havingformed a mercury halide, which may be as an insoluble halogen salt inwater which is removed in the scrubber. In an aspect, the mercury halideis scrubbed out in the scrubber and thereafter disposed.

In an aspect, the invention further includes a cleaning step for thefurther processing of the generated fuel gas. Such step may be referredto as a “wet scrubbing” step. In an aspect, the gas is introduced as agas flow into a wet scrubber for purification. In an aspect, the gasscrubber(s) separate tars, oils and Char from the product gas flow. In afurther aspect, the gas scrubber(s) can further cool the product gas,for example to a temperature below about 80° C. The scrubber(s) mayfurther be employed for a final removal step for any toxic compounds inthe fuel gas product.

In an aspect, the produced fuel gas/water vapor mixture enters the gascleaning, i.e. scrubber system. In an aspect, each reactor line has itsown first gas cleaning unit. The gas streams are combined after thefirst scrubber units and will enter the additional scrubbers afterwards.

In an aspect, the gas cleaning units include or consist of scrubbers,vessels, pumps, oil discharge units and heat exchangers. Water combinedwith additives, such as for example an alkalinity source (e.g. NaOH) orother source such as limestone for removal of sulfur, which are known tothose skilled in the art of incineration technologies. Notably, theheating methods according to the invention are distinct fromincineration as external heating is provided. For clarity, the methodsof the invention do not employ incineration. Those skilled in theincineration arts understand scrubbing using water containing alkalinematerials to remove acidic components are distinct methods. These areused in a closed loop system to clean condensates and contaminants outof the gas stream and to cool the gas down. The condensates containolefins, aromatics and paraffins as solids and water. The standardsystem includes or consists of five gas cleaning systems. This amountcan be reduced or increased depending on the feedstock specificationsemployed according to embodiments of the invention. The scrubbedcomponents like tar will be the feedstock of the cracking reactors, thelight oil fraction of aromatic oil and olefins will be separated fromthe solids/water and reprocessed in the gasification system and thewater will be pre-cleaned and reused.

In an aspect, the invention converts the e-waste sources into a Charsource and a Clean Fuel Gas source. In an aspect, the invention willfurther include a recycling step for the recycling of any oils and tarscreated from the methods described herein. In an aspect, the recyclingof the oils and tars involves cracking them and then reprocessing theshorter chain molecules into a main reactor to be converted intoadditional Clean Fuel Gas. In a beneficial aspect of the invention, suchgenerated Clean Fuel Gas is suitable for use in maintaining operation ofthe processes of the invention at a point of use (i.e. facilityemploying the methods, systems, and/or processes of the presentinvention).

In an aspect, the invention further includes a separation step for thefurther processing of the generated Char source (as shown in FIGS. 8 and9). In an aspect, the Char source generated according to the inventioncomprises metals in a fine metallic state. In a further aspect, the Charsource generated according to the invention comprises glass fibers (suchas from FR4 boards), carbon particulates/fine matter, metals, preciousmetals and/or combinations of the same. The Char source will furtherundergo a subsequent separation step, such as to remove a desiredcomponent from the Char as may be accomplished by a variety ofcommercially-known processes.

In one embodiment, a carbon conversion unit can be employed to removecarbon from a Char source. Beneficially, the generated Char source hasundergone about a 40%, 50% or greater reduction (weight basis) as aresult of the thermolysis processing according to the invention whichremoves the organics and thereafter can be further separated theremaining components. In an aspect it is desirable to remove additionalcarbon from the Char source, such that there is a great than 50% (weightbasis) reduction of carbon in the Char source. In a preferredembodiment, the carbon is reduced to less than 10% (weight basis). In apreferred embodiment the carbon is removed from the Char source.

In an aspect, the further processing of the Char source can include theuse of ozone to convert carbon to a fuel gas (in the form of carbondioxide or carbon monoxide which thereafter are further processedthrough the scrubbers). In such an embodiment, ozone can be added to achamber containing the Char (at either room or ambient temperature or atelevated temperatures, such as about 100° C. to about 300° C.). Such achamber could be one of the reactors or a separate chamber. In anaspect, the use of ozone to convert carbon to a fuel gas obviates theuse of a cold incineration process.

In an aspect, the further processing of the Char source incinerates thecarbon in the residue at controlled temperatures, such as from about300° C. to about 500° C. The air supply is temperature controlled andthe whole process can be cooled, such as to a temperature from about300° C. to about 500° C. Such process is referred to as a coldincineration process). In an aspect, the equipment includes or consistsof an infeed screw conveyor, a rotary calciner with flights and registerpipes for heat transfer, a cooled exit screw conveyor, exhaust gascleaning unit with particulate removal and optional scrubbing devices.

In an aspect, the infeed screw conveyor has a conventional design andthe temperature of the co-product is the main parameter for itsspecification. The temperature of the co-product will be increased byindirect heating and controlled air supply before it enters the rotarycalciner.

In an aspect, the rotary calciner has a basic design of an elongateddrum with two bearings, an inner drum with flights and a central outputscrew conveyor. Input and output are symmetrical located. The drive isat the head of the rotary calciner. Input and output of the material isdone via the shaft and thus gas proof to the atmosphere. A pipe registerin two levels inside the drum will cool the process. The material can betransported by the inner flights into the output screw conveyor. Thematerial can be continuously transported through the rotary calciner ata constant temperature and constant cooling. Moreover, carbon oxidizesto CO₂ in this process.

In an aspect, the output screw conveyor has a conventional design with acooling jacket and connected to the storage vessel.

In an aspect, the exhaust gas cleaning module has a conventionalparticulate removal system and can be optionally equipped with a gasscrubber with solid removal. A fan can be added if necessary beforeentering the stack.

In an aspect, a separation step is employed to remove the fine metalsand/or the glass fibers from the Char. In an aspect, the glass fiberscan be separated resulting in a highly concentrated metals/Char mixture.In an aspect, the removal of the glass fibers provides a 2× concentratemetals/Char mixture, or a 3× metals/Char mixture, or preferably a 4×metals/Char mixture. Beneficially, the metals/Char material can beprocessed in domestic refineries in the processed condition as opposedto requiring off-shore shipment to international smelters. As a furtherbenefit, the metals in Char mixture can be recovered by refining whilefurther removing the fiberglass, such that each component separated fromthe Char remains substantially-free or free of the toxic components(such as dioxins and furans). Such refining and removal of fiberglassare achieved through known separation methods (such as screen andgravity separation) which are able to separate metals, includingprecious metals, which are recovered substantially in their originalform. Moreover, the separated metals have not been melted in theprocess, or a majority of the metals have not been melted, whichpreserves the value of the metals.

In an aspect of the invention, at least 50% recovery of the metals,including precious metals (e.g. gold, silver, palladium), electronicmetals (e.g. copper, aluminum), and rare earth metals are recovered fromthe Char through separation methods, preferably at least about 55%,preferably at least about 60%, preferably at least about 65%, preferablyat least about 70%, preferably at least about 75%, preferably at leastabout 80%, preferably at least about 85%, preferably at least about 90%,or most preferably at least about 95%. Examples of separation techniquesincludes, for example, mechanical (i.e. shaking) separation,electrochemical processing, or the like. In an exemplary embodiment ofthe invention, gold in the Char (containing the metals and glass) wasrecovered at above 90%, above 95% and in most preferred embodimentsabove 98%. In an aspect of the invention, the extracted metals can befurther purified for a desired application of use. Because the preciousmetals are in their native form and not alloyed, chemical andelectrochemical processes can be used to recover them individually byother known processes.

In an aspect, the fuel gas is transported through the gas cleaningsystem by increasing the pressure, such as to about 100 mbar byventilation systems. In an aspect, 100 mbar is the limit value for thesystem employed according to the invention.

In an aspect, the wastewater treatment includes or consists of aphysical and biological treatment segment. The wastewater can bedischarged after pre-treatment and cleaning.

In an aspect, the safety system transports the fuel gas to a flare incase of an emergency. In an aspect, all the pipelines have valves, whichautomatically open in case of a power failure. In a further aspect, theconnecting pipes to the flare are equipped with burst discs, which willprevent excessive pressure in the reactors and the gas cleaning systems.In case of an emergency, this system will help to shut down the systemin a safe manner.

Optional Additions for Enhanced Processing and Efficiency of ThermolysisMethods

The methods of the present invention are suitable for combination withadditional inputs to further maximize the efficiency of the methods andsystems employed. It is known that power generation equipment isdesigned to perform at best efficiencies for converting the suppliedfuel into power at a specified range of fuel load. This range for gasturbines and gas engines is generally in the 80% to 100% fuel gascapacity of the selected gas turbine or gas engine. Efficiency isdetermined as thermal energy required in the fuel gas to generate powerand provided by the vendors in BTU/kWh valid for the specified range of80% to 100% capacity fuel gas load of their equipment. As one skilled inthe art will ascertain, fuel gas loads of <80% will decrease theefficiency of converting the thermal energy of the fuel gas into power.

According to optional embodiments of the invention, the clean fuel gassource output according to the methods of the invention can be furtherenhanced, such as measured on a cfm (cubic feet per minute) and theheating value of the clean fuel gas source constantly controlled inBTU/cuft. The quantity and the heating value of the clean fuel gassource are dependent on the feedstock properties processed according tothe embodiments of the invention. A homogenous feedstock Input into thereactors will yield a consistent clean fuel gas source Output for bothparameters: cfm and heating value per cuft supplied to a gasturbine/engine. Fluctuations in the feedstock will change the quantityof the generated clean fuel gas source and its heating value per cuft.Accordingly, the methods of the invention may be further controlled forthe output of clean fuel gas source by adding Natural Gas in apre-mixing storage vessel with the clean fuel gas source beforesupplying it as fuel, such as to a gas turbine/engine.

In an aspect, the addition of natural gas (such as methane) to the cleanfuel gas source output of the invention has various advantages. Theadded Natural Gas can equalize any fluctuations in the gas flow quantityof the clean fuel gas source and the blend of the two combined gasstreams will ensure the necessary supply of total gas to a gasturbine/engine to achieve the 80% to 100% fuel gas load for optimizedperformance of the power generation equipment. In addition, addingNatural Gas to the available clean fuel gas source capacity can increasethe total capacity of power generation at a project site. Still further,substituting the clean fuel gas source by Natural Gas during maintenanceperiods of the systems employed provides a redundancy in powergeneration for the duration of the shut-down of the system.

Additional sources of fuel can be utilized in the methods of theinvention, including those listed below as “Additional Fuel Sources”with the exemplary BTU for each input source.

Generated Outputs of the Thermolysis Methods

In an aspect, the methods, systems, and/or processes of the presentinvention convert the e-waste sources into a Char source and a CleanFuel Gas source. Beneficially, the hydrocarbon materials from thee-waste input are converted to the Clean Fuel Gas while the metals andcarbon-coke will be collected as “Char.” As a further benefit, any oilsand tars created are recycled into the secondary reactor and crackingreactor to be converted into additional fuel gas, such as may beemployed to maintain operation of the processes of the invention at apoint of use (i.e. facility employing the methods, systems, and/orprocesses of the present invention).

Char

The methods according to the invention employing the thermolysis methodsbeneficially provide a processed Char comprising glass fibers (such asfrom FR4 boards), carbon particulates/fine matter, metals, preciousmetals and/or combinations of the same. In an aspect, the Char is anon-hazardous material. In an aspect, the Char is substantially-free orfree of toxic chemicals. The Char must be cooled down before opening toair to prevent formation of hazardous dioxins and furans (such as forexample to less than about 120° C.).

In an aspect, the Char is substantially-free of halogen compounds. In afurther aspect, the Char is substantially-free of toxic chemicals andhalogen compounds. In an aspect, the Char is free of toxic chemicals,including for example mercury-containing compounds. In an aspect, theChar is free of halogen compounds. In a further aspect, the Char is freeof toxic chemicals and halogen compounds.

Fuel Source

The methods according to the invention employing the thermolysis methodsbeneficially provide a clean fuel source. In an aspect, the fuel gassource is a clean, non-hazardous material. In an aspect, the fuel gassource is substantially-free of toxic chemicals. In an aspect, the fuelgas source is substantially-free of halogen compounds. In a furtheraspect, the fuel gas source is substantially-free of toxic chemicals andhalogen compounds. In an aspect, the fuel gas source is free of toxicchemicals. In an aspect, the fuel gas source is free of halogencompounds. In a further aspect, the fuel gas source is free of toxicchemicals and halogen compounds. In an aspect, the fuel source issubstantially-free or free of polycyclic aromatic hydrocarbons (PAHs),halogenated dibenzodioxins, halogenated dibenzofurans, biphenyls, and/orpyrenes.

In an embodiment, the fuel gas generated is utilized for heating thereactor(s) for the system and methods of the thermolysis methods of theinvention. In an aspect, the heat for the reactor(s) is supplied byabout 10-50% of the generated fuel gas, about 10-40% of the generatedfuel gas, or about 20-30% of the generated fuel gas.

In an embodiment, the fuel gas generated has a composition as set forthin the Tables in the examples.

In an aspect, the fuel gas is a superior product as a result of no airor external oxygen introduced into the reactors, such as is common inpyrolysis and/or partial oxidation systems.

In an embodiment of the invention the thermolysis of e-waste sourcescontain from about 3,000 to about 19,000 BTUs per pound of e-waste,producing a Clean Fuel Gas as an energy source. As one skilled in theart will ascertain based on the disclosure of the invention set forthherein, differences in e-waste sources will impact the BTUs per pound.In an aspect, a thermoplastic housing e-waste source may include, forexample, from about 14,000-16,000 BTUs per pound.

According to still further aspects, various waste sources will providethe following estimated BTU/pound:

HIPS 17,800 FR HIPS 15,850 ABS 16,350 FR-ABS 14,800 FR PWB Laminate5,140 PMMA-Acrylic 10,750 Composite Resins 12,850

In an aspect, the heating value of the generated fuel gas source willvary accordingly based on the type e-waste input source. For example, ina non-limiting embodiment, the heating value of fuel gas generated fromthe following input sources according to the data generated in theExamples is approximately 400 Btu/ft³to 800 Btu/ft³. In other aspectsthe heating value can be modified based on the inputs to provide rangesfrom about 200 Btu/ft³ to about 1500 Btu/ft³ or from about 500 Btu/ft³to about 1000 Btu/ft³. In an aspect, notably, the evaluated fuel gas metall emission requirements evaluated.

In an aspect, the generation of the fuel gas is suitable for variousapplications of use. In an embodiment, the generated fuel source can beused to generate electricity using engines or gas turbines to power amanufacturing plant and/or boilers as a replacement for natural gasand/or electricity. In another aspect, the fuel gas can be used forburners, or steam and electricity production and/or distribution. Manyexamples of such uses are well known to practitioners of the art.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

The disclosure of each reference set forth herein this patentapplication is incorporated herein by reference in its entirety.

Example 1

Assessment of various e-waste sources according to embodiments of theinvention were conducted to review and analyze the mixture of e-wastesources as inputs for processing. The following e-waste sources wereanalyzed and summaries of the assessment of inputs follows:

1. Keyboard and Mouse Study:

E-waste component Weight (pounds) Dell ® wired keyboard mfg. in 2002 PWB(power, main, and key boards) N/A (small) Plastic covers, base, keys &cable 1.5 Microsoft ® wired mouse mfg. around 2001 Clam shell enclosure0.05 Wire 0.01 Keyboard 1.5 Mouse 0.1 TOTAL 1.5 Part Weight (Lbs) BTUValue/lb. Total BTUs ABS Housing 1.1 16,350 17,985 PVS Wires 0.1 8,250825 FR-4 PWBs & Mylar 0.1 5,140 514 Nylon connectors 0.1 12,500 1,250Plastics Totals 1.4 20,574 Metal parts & frames 0.1 BTU/lb. of Plastics14,696 Total Weight ib. 1.5 Part Weight (Lbs) BTU Value/lb. Total BTUsHIPS Housing 0.1 17,800 1,780 PVC Wire & Connector 0.1 8,250 825 FR-4PWBs & Mylar 0.1 5,140 514 Plastics Total 0.3 3,119 Copper wire 0.1BTU/lb. of Plastics 10,397 Total Weight ib. 0.4

2. HP Deskjet® 970 CSE Study:

Part Weight (Lbs) BTU Value/lb. Total BTUs FR-ABS Housing 9.5 14,800140,600 PVC Wires & plugs 0.5 8,250 4,125 FR-4 PWBs 0.5 5,140 2,570FR-Nylon connectors 0.1 12,500 1,250 Plastics Totals 10.6 148,545 Metalparts & frames 2.5 BTU/lb. of Plastics 14,014 Total Weight ib. 13.1E-waste component Weight (pounds) HP Deskjet ® in jet printer mfg. in2002 PWB (power, main, and key boards) 0.5 Plastic covers, end caps,lids, base, etc. 9.5 Metal frame, carriage support & brackets 2.5 Wireharness, connectors & terminals 0.5 TOTAL 13.0

3. DVD Materials Study:

E-waste component Weight (pounds) Samsung ® DVD unit PWB (3 large, 5small boards 0.25 Metal housing 0.70 Polymeric materials combined 1.4 45screws and mounting clips 0.01 165 surface mounts and components 0.1TOTAL 2.46

4. Linksys® Wireless Router Study:

E-waste component Weight (pounds) Linksys ® router unit mfg. in 2002 PWB(power, main, and key boards) N/A (small) Plastic covers, base, keys andcable 1 Wires and antennas 0.2 TOTAL 1.2 Part Weight (Lbs) BTU Value/lb.Total BTUs FR-ABS Housing 0.7 14,800 10,360 PVC Wires & Antenna 0.28,250 1,650 FR-4 PWBs 0.1 5,140 514 FR-Nylon connectors 0.1 12,500 1,250Plastics Totals 1.1 13,774 Metal parts & frames 0.1 BTU/lb. Of Plastics12,522 Total Weight ib. 1.2

5. Flat Screen Display (FSD) Study:

E-waste component Weight (pounds) Dell ® E178 FPc 17 inch LCD displaymfg. in May 2008 PWB (power, main, and key boards) 0.5 CCFL (coldcathode fluorescent lamp) 2 N/A (small) glass lamps Plastic back covers1.0 Metal frame, backing and support brackets 3.5 Base and support(metal and polycarbonate) 2.5 Wires harness, connectors and terminals0.5 TOTAL 8.0 Part Weight (Lbs) BTU Value/lb. Total BTUs FR-ABS Housing4.4 14,800 65,120 PVC Wires & plugs 0.5 8,250 4,125 FR-4 PWBs 0.5 5,1402,570 FR-Nylon connectors 0.1 12,500 1,250 Acrylic screen 0.2 10,7502,150 Plastics Totals 5.7 75,215 Metal parts, frames & 2.5 BTU/lb. OfPlastics 13,196 CCFL Total Weight ib. 8.2

Example 2

Systems and apparatus for processing e-waste sources. Apparatus andprocessing system for PWBs were evaluated for the assessment of productfeatures and material balances as disclosed pursuant to the embodimentsof the invention. The target of the test was to prove the technicalcapabilities of a plant with a continuous feed of the delivered PWBs andto yield specific product and operating parameter for furtherevaluation. The methods according to the invention were evaluated toconfirm gas output having a suitable composition with high methane,hydrogen and carbon monoxide content for further usage, and hydrogenbromide or hydrogen chloride neutralized in the gas scrubbers withsodium hydroxide. The methods according to the invention were evaluatedto confirm complete destruction of dioxins, including dioxin content inthe Char as non-detectable, despite original dioxin content contained inthe PWB feedstock. The methods according to the invention were evaluatedto confirm complete destruction of VOCs and other toxic components,along with the measurement of any potentially hazardous components andVCOs to assess suitability of the processes for use in factories. Themethods according to the invention were evaluated to assess ability tocollect metal particles from the Char through mechanical separation.

Parameters of the test operation. 1000 pounds of PWB feedstock wasreceived and inspected. The feedstock had been shredded to <2 inches forthe test. The reactor substantially as depicted in FIG. 1 had beencleaned before the test. Process software and sensors were adjusted torecord the operating conditions. The material handling and infeedconditions were adjusted before the test. Technical adjustments for thisspecific feedstock were implemented as outlined below.

Continuous processing. A continuous plant operation was conducted afterheating the system up with controlled feedstock input and productdischarge. The operating parameters were adjusted to the requirements ofthe feedstock. The resulting materials and media were sampled anddocumented. A total of three gas samples, a feedstock sample and a Charsample were obtained for further analysis. The analysis of the sampleswas carried out by a certified independent laboratory.

Standard operating conditions of the plant included the followingpreparation of the plant for the operation: Start-up of the plant: 6:30am; Feedstock Input: from 11:00 am; Sampling between 13:00 and 15:30 pm;Completion of plant operation: until 18:00 pm; Discharge of products andmedia, Recording of the yielded products for the mass balance.

General conditions. The feedstock had been shredded and was fedaccording to the test protocol. The start-up process included theheating of the reactors and the adjustments of the gas scrubbing unitsand adjacent plant components. The operating conditions were adjusted tothe test plant as outlined below.

Plant conditions. The plant operation during the test used the standardconfiguration of the system and used specific adjustments for thisfeedstock—These adjustments included:

Plant operation with the lower burner only;

Feedstock infeed periodically as infeed chamber emptied;

Reactor conditions with temperatures of 630° C. at the reactor top and750° C. to 850° C. at the lower parts of the reactor;

Release of the gas from the gas dome to scrubber 1, no direct connectionfrom the reactor head to scrubber 4;

Steam generation via heat exchanger and injection of the steam throughspecial pipelines directly into the reactor head;

Cracker-module for generated condensates was not in operation, becausethe volume of these oils was too low for an efficient operation; and

The operation of the gas scrubbers was carried out withoutrecirculation; Level control in scrubber 1 and 2 by manual adjustmentsof the correct level; and Control of the oil water separator between thescrubbers and the gas pipeline of the plant during operation.

Special conditions of the test operation. The selected basic operatingparameters were continuously monitored and needed only minisculeadjustments. The Infeed volume of the feedstock was increased during thesecond phase of the test. The feedstock input was continuous—in selectedintervals. Due to the high reactivity and fast gasification of thefeedstock, a pulsating increase in gas volume and pressure wasmonitored. This effect had no negative impact for the test operation. Anincrease of feedstock caused more gas generation and the slight pressureincrease in the range of a few millibar had no impact on the testoperation.

The water content in the reactor was slightly increased by steaminjection, which increased the gas generation due to the chemicalbalance reactions. The gas volume was constantly measured. The generatedgas volume during phases of increased feedstock supply was 30 m³/hr. andabove, the average value was ca. 20 m³/hr.

The scrubber operated at normal stationary conditions. The differentialpressure was in the range like differential pressure in previous testruns from about 20-50 mbar.

No recirculation and injection of the generated oils from scrubbers 1and 2. The low amount of oil components was removed from scrubbers 1 and2 and collected.

The level control of the media during operation were adjusted constantlyto its range level. Media in the first scrubber: oil, Media in thefollowing scrubbers: water with additives. All generated media wereremoved after the test and measured for the mass balance.

No special technical adjustments were necessary during the testoperation from the plant conditions described above. No technicalfailures occurred. The plant operated perfectly stably and itscapability proven to process this feedstock.

Summary of apparatus and process set-up. The feedstock reacts quickly inthe main reactor at these temperature conditions and gasifies rapidly.This gasification profile was monitored by the pressure increase shortlyafter the feedstock was fed into the system. The observed pressureincrease is not critical and can be equalized by a more constantfeedstock input for a commercial size unit. Beneficially, thegasification and reaction speed of the tested feedstock described hereinenables a high throughput volume. The generated gas is piped from thereactor into the gas scrubbing units, which remove the condensates fromthe gas stream. The condensates are then collected in scrubber 1 and 2and their viscosity is suitable for reinjection into the process as afuel source. Residual tars are not left over in the scrubbers.

Various operational parameters were adjusted including: throughputvolumes for the Infeed screw conveyors; adjustments of the steaminjections to balance out the reactions in the reactor; reactortemperatures; volume of feedstock input; and residence time dependent onChar removal. With these adjustments and the set-up described a stableplant operation was achieved.

Example 3

Exemplary plant operation for PWB feedstock processing. Following theassessment of the apparatus and systems set-up in Example 2, the plantoperations were utilized to process e-waste feedstock.

The delivered feedstock material had been shredded to <2″ for the testrun and continuously fed into the plant in short intervals. Steam wasinjected, condensates were removed from scrubbers 1 and 2 and Charremoved from the Char screw conveying unit.

The infeed specifications of the screw conveyors for this material whichhad not been previously processed was tested during start up anddecreased the infeed volume shortly during Phase 1. The infeed volumewas also decreased later during the test, because the temperature in theChar collection drum increased rapidly and more time was needed to cooldown the Char. The cool down period is necessary to avoid chemicalreactions outside of the plant configuration. The delay in thetemperature cool down was caused by the heat capacity of the Char-metalmixture of this specific feedstock. The infeed rate depends on thedesign of the system and is a parameter that is optimized.

TABLE 1 Summary test operations Plant operation volumes Input - total170 kg Average throughput after deduction of the 35 kg/h cool down phase

The temperature and pressure measurements are shown in FIGS. 16-17(measured in degrees Celsius) where Temperature 1 is the middle part ofreactor; Temperature 2 is at the reactor head; and Temperature 3 is atthe gas dome (FIG. 16) and Pressure (mbar) compared to flow rate isshown (FIG. 17).

Evaluation of the measured values and data. The plant was operated withan elevated temperature range in the reactor (>700° C.) to secure acomplete chemical conversion of the e-waste input. The pressure in thereactor was on average >5 mbar. Significant pressure spikes were notrecorded despite the high reactivity and rapid gasification of thematerial. Slight temperature adjustments were done during the test. Thegenerated gas volumes had significant spikes due to high reactivity ofthe material, which could be equalized by a more constant infeed volume.The pilot plant would require a different infeed system for thisfeedstock and a much higher throughput could be achieved. This wouldalso require additional equipment at the pilot plant to secure a fastcool down of the Char-metal mixture without air intrusion. The materialinfeed in intervals with the resulting increased gas generation isrecorded in the first phase of the test. The throughput reduction laterduring the test was caused to increase the cool down time of the Char.These effects are not relevant for the test plant technology, buthelpful for the total process evaluation. Different volumes of steaminjection, such as from about 5 wt.-% to about 10 wt.-%, during thistest did not influence the overall process data. Steam is added tocontrol the moisture content of the incoming material stream. It isgenerated from process heat.

The reactor head temperatures measured between about 600° C.-800° C.These temperatures can be achieved also with a higher throughput as itwill be regulated by the heat transfer capabilities of the Char.

Temperature control and the volume of scrubbed out components arerelevant for the evaluation of the data from the gas scrubbing units.The temperature of scrubber 1 was regulated at ca. 75° C., scrubber 2and 3 at 30° C. Media (oil or water in the scrubbers with any additives,such as alkalinity sources and/or stabilizers) were added to control thetemperatures and filling level of the scrubbers. The condensates inscrubber 1 were long-chained hydrocarbons, which will be reinjected intothe reactor. Water and aromatics were scrubbed out in scrubber 2.Process water without oil components were scrubbed out in No 3.

Explanations to the test operation. The reactivity of the test materialwas unknown. The Char-metal mixture with a high specific heat capacityrequired a longer cool down period than other previous tested feedstock.The gas production was pulsating due to the high reactivity of thefeedstock, which caused no problems during the test at the pilot plant.

Sampling, Analysis, Evaluations. The feedstock and the Char samples werecollected and analyzed. An additional analytical test for dioxins in thefeedstock and Char was ordered. The gas samples were collected inspecial gas bottles and sent to the laboratory for external testing. Thegenerated oil volume was very small and therefore was not analyzed. Theoil samples were collected and available for analysis. The test sampleswere delivered to the laboratory after the test run for analysis. Theanalysis was done by using one representative sample and the conditionsof different feedstock content could not be evaluated at this test.

Analysis data and M+E Balance. The results of the analysis are shown inTables 2-4.

TABLE 2 Mass balance Output Input Oil/ Input Steam Gas Oligomeres CharWater Mass [kg] 170 23 64 3 108 15

TABLE 3 Analysis feedstock material Analysis parameter Value DimensionDry residue (TR) 99.2 Ma.-% HF-Digestion Iron 5860 mg/kg Aluminum 22500mg/kg Copper 352000 mg/kg Zinc 778 mg/kg Tin 92100 mg/kg Cadmium 0.18mg/kg Chromium 21.4 mg/kg Nickel 5630 mg/kg Lead 24000 mg/kg Bromine20000 mg/kg Heating value 8185 kJ/kg Chlorine 1.13 Ma.-%

TABLE 4 Dioxin Analysis parameter Dimension BG Value 2,3,7,8-TetraCDDng/kg TS 1 <1 1,2,3,7,8-PentaCDD ng/kg TS 1 <1 1,2,3,4,7,8-HexaCDD ng/kgTS 1 <2 1,2,3,6,7,8-HexaCDD ng/kg TS 1 <3 1,2,3,7,8,9-HexaCDD ng/kg TS 1<5 1,2,3,4,6,7,8-HeptaCDD ng/kg TS 5 <15 OctaCDD ng/kg TS 10 <2002,3,7,8-TetraCDF ng/kg TS 1 <1 1,2,3,7,8-PentaCDF ng/kg TS 1 <22,3,4,7,8-PentaCDF ng/kg TS 1 <2 1,2,3,4,7,8-HexaCDF ng/kg TS 1 <21,2,3,6,7,8-HexaCDF ng/kg TS 1 <1 1,2,3,7,8,9-HexaCDF ng/kg TS 1 <12,3,4,6,7,8-HexaCDF ng/kg TS 1 <1 1,2,3,4,6,7,8-HeptaCDF ng/kg TS 3 <51,2,3,4,7,8,9-HeptaCDF ng/kg TS 3 <3 OctaCDF ng/kg TS 10 <15 SumPCDD/PCDF (WHO TE ng TE/kg (n.b.*) 2005) TS

The results shown in Tables 2-4 analyzed a representative sample fromseveral collected samples. The analysis of an additional sample withlarger metal particles yielded much less overall metals and cannot beconsidered as a representative sample. This analysis had an elevatedlevel of Zn. The selective reduction of glass fiber particles increasesthe amount of metals and will not yield a representative sample.

The flame and/or fire retardants in the PWB feedstock are known tocontain Bromine, which was analyzed at 2% in the feedstock. The analysisof the dioxins in the feedstock showed elevated levels of dioxins in thefeedstock. Target of the test was to avoid creating new dioxins andreduce existing dioxins by cracking.

Analysis of the Product Gas. The results of the analysis are shown inTable 5.

TABLE 5 Product Gas (in Volume percentage) Main Components Gas Gas[Vol-%] 7_1_31 7_1_33 H₂ 36.4 34.1 O₂ 0.30 0.31 N₂ 1.70 1.9 CH₄ 22.222.5 CO₂ 11.2 10.3 CO 20.8 21.5 Ethane 0.66 1.0 Ethene 2.5 2.6 Propane<0.01 0.01 Propene 0.06 0.15 i-Butane <0.01 <0.01 n-Butane <0.01 <0.01Heating value 4.8 4.9 [kWh/m³]

The samples of the generated gas were collected in Phase 1 and Phase 2(13:50 and 15:50). The analysis results reflect homogeneous operatingconditions. The gas analysis shows relatively high Hydrogen content andlow paraffin content. The ratio of CO and CO2 is characteristic for thistemperature profile. Oxygen and Nitrogen are not components of theoriginal gas compositions, but intruders into the gas sample during thetransport of the glass vessels.

The molecular structure of the feedstock with characteristic Phenolcomponents will not generate significant amounts of long chainedmolecules like paraffins and olefins. The aromatic components of the gasvapor will not be totally cracked without the cracking reactor and willgenerate a liquid fraction with low viscosity. The low amount ofgenerated oily components can be pumped at average temperatures and canbe converted with the cracking reactor.

Analysis of Char-Metal mixture. The results of the analysis are shown inTables 6-7.

TABLE 6 Char-Metal mixture Analysis parameter Value Dimension DryResidue (TR) 99.6 Ma.-% Carbon, raw 9.1 Ma.-% Heating value, raw 4032kJ/kg HF-Digestion Iron 51900 mg/kg Aluminum 18600 mg/kg Copper 172000mg/kg Zinc 21600 mg/kg Tin 9800 mg/kg Cadmium 1.54 mg/kg Chromium 74.9mg/kg Nickel 19400 mg/kg Lead 2670 mg/kg Silver 1.69 mg/kg

As shown in Table 6, the analysis results for the Char-metal mixture donot reflect the complete composition of the Char. The non-ferrous metalsAl, Sn, Zn, and Cu are significantly too low. The analysis of thecollected samples differs by a factor of 50%, which is based upon anuneven distribution of the content and particle size. Larger pieces ofmetals were found in the Char, which either agglomerated or melted.These agglomerations have to be added and were not shown in the analysisdata.

TABLE 7 Dioxins Analysis parameter Dimension BG Value PCDD/PCDF2,3,7,8-TetraCDD ng/kg TS 1 <1 1,2,3,7,8-PentaCDD ng/kg TS 1 <11,2,3,4,7,8-HexaCDD ng/kg TS 1 <1 1,2,3,6,7,8-HexaCDD ng/kg TS 1 <11,2,3,7,8,9-HexaCDD ng/kg TS 1 <1 1,2,3,4,6,7,8-HeptaCDD ng/kg TS 5 <5OctaCDD ng/kg TS 10 <10 2,3,7,8-TetraCDF ng/kg TS 1 <21,2,3,7,8-PentaCDF ng/kg TS 1 <1 2,3,4,7,8-PentaCDF ng/kg TS 1 <11,2,3,4,7,8-HexaCDF ng/kg TS 1 <1 1,2,3,6,7,8-HexaCDF ng/kg TS 1 <11,2,3,7,8,9-HexaCDF ng/kg TS 1 <1 2,3,4,6,7,8-HexaCDF ng/kg TS 1 <11,2,3,4,6,7,8-HeptaCDF ng/kg TS 3 <3 1,2,3,4,7,8,9-HeptaCDF ng/kg TS 3<3 OctaCDF ng/kg TS 10 <10 Sum PCDD/PCDF (WHO TE ng TE/kg (n.b.*) 2005)TS

As shown in Table 7, the Char has been analyzed for Dioxin content. Mostmeasured data were below detection limit (data in the table are thedetection limits and not the actual measured data of the Char). Theanalysis demonstrates that dioxins were not generated and that evenexisting dioxins in the feedstock were cracked during this test underchemical reducing conditions. A comparison of the dioxin values in thefeedstock and the Char confirms the complete destruction of the dioxinmolecules. Notably, the further destruction through cracking can beobtained by optimizing a feedstock processing by additional reactors tosecure complete cracking by follow up reactions.

Overall results. The plant operation with the delivered feedstock wassuccessful. The technical design of the pilot plant demonstrated thedesired processing of the PWB feedstock. A gas for multiple applicationshas been generated and a Char-metal mixture suitable for furtherprocessing was obtained. Further benefits include the confirmation thatno dioxins generated and existing dioxins cracked, confirming reductionto practice of not creating any toxic materials resulting from thebrominated flame and/or fire retardants in the PWBs. Accordingly, thepilot plant demonstrated a stable performance with neither thecomposition of the plastics nor the metals having any negative impact onthe process.

Example 4

A quantitative assessment of Char source generated according to themethods of the invention was conducted to assess the metals and otherelements present in the Char source. The Char source was ground in a rodmill and then screened to separate based on size of the particulatematter. The undersize was the put through a shaking table. The tabletails were then tested on a centrifugal separator for separation of theprecious metals. Following separation of the metals and other elementsthe amounts from the mass balance are shown in either a % or ppm. Theresults are shown in Tables 8A-8C.

TABLE 8A Sample Au Pd Pt Ag As B Ba Be Bi Cd Ce Co Cr Cs Number (g/t)(g/t) (g/t) ppm Al % ppm ppm ppm ppm ppm Ca % ppm ppm ppm ppm ppm Cu %Fe % 106104 9,180.10 228.77 1.62 662 1.03 157 239 5,777 18.7 143 0.107.8 3.7 91 215 <0.5 58.95 15.30 106105 502.30 33.86 0.13 183 2.60 27 129679 60.0 50 0.20 2.8 0.6 354 79 <0.5 62.38 5.03 106106 1,363.68 94.150.39 125 3.00 10 576 5,164 15.1 78 0.63 4.4 4.0 139 153 <0.5 41.82 7.40106100 299.37 35.80 0.13 86 4.43 8 2,365 1,356 30.5 41 2.17 4.0 7.9 114116 <0.5 24.60 4.97 106149 1,537.15 44.87 0.39 176 2.83 56 145 5,95886.7 43 0.20 3.1 1.8 264 144 <0.5 70.52 5.97 106150 283.53 60.37 0.31126 3.5 16 2,981 2,184 6.1 46 2.97 4.4 8.9 122 342 <0.5 18.43 7.67106151 1,009.09 61.21 0.30 214 8.80 77 319 9,336 18.2 51 0.40 3.8 5.2205 142 <0.5 62.16 5.60 106152 337.84 71.36 0.33 124 3.17 11 2,199 2,5736.2 56 2.20 4.5 7.5 164 277 <0.5 22.52 9.80 106153- 3.32 8.77 0.07 864.90 24 8,258 1,197 7.7 23 7.95 5.4 18.3 26 91 1.2 2.50 1.95 4 123.7014.62 0.08 66 3.15 14 4,420 1,049 9.7 22 4.25 3.4 10.2 46 272 34.19 4.87

TABLE 8B Sample Ga Ge Hf Hg In La Li Mn Mo Nb Ni P Pb Rb Re Number ppmppm ppm ppm ppm K % ppm ppm Mg % ppm ppm Na % ppm ppm ppm ppm ppm ppm106104 6.1 6.5 4.5 0.15 62 <0.1 2 10 <0.1 1,758 74.3 <0.1 7.60 21,438192 29,479 1 0.02 106105 4.2 2.6 0.2 <0.1 28 <0.1 <2 <1 <0.1 868 72.0<0.1 0.55 33,721 163 18,543 <1 0.01 106106 4.1 1.7 3.9 <0.1 25 <0.1 2 2<0.1 3,374 54.6 <0.1 4.35 18,970 133 17,786 <1 0.01 106100 5.7 1.0 0.7<0.1 12 <0.1 4 8 0.1 1,808 50.5 0.1 1.77 12,798 164 6,832 1 0.01 1061496.1 2.9 1.9 <0.1 30 <0.1 <2 1 <0.1 1,768 175.0 <0.1 2.90 36,803 1699,866 <1 0.02 106150 6.4 0.9 0.8 <0.1 17 <0.1 5 11 0.1 5,868 19.8 0.11.05 10,722 184 8,408 1 <0.01 106151 13.0 3.4 4.8 <0.1 26 <0.1 <2 2 <0.13,373 335.3 <0.1 8.10 10,748 158 8,814 <1 0.01 106152 5.7 0.8 0.8 <0.117 <0.1 4 7 0.1 8,524 7.9 0.1 0.55 13,152 107 9,759 <1 0.01 106153-410.0 <0.5 0.5 <0.1 2 <0.1 10 29 0.3 1,714 11.8 0.3 0.75 1,823 383 4,7803 <0.01 6.0 0.3 0.5 <0.1 5 <0.1 15 1,332 16.3 0.2 0.79 4,474 221 4,731<0.01

TABLE 8C Sample Sb Sk Se Sr Ta Te Th Tl U V W Y Zn Zr Number S % ppm ppmppm Sn % ppm ppm ppm ppm Ti % Ppm ppm ppm ppm ppm ppm ppm 106104 0.1016,955 3 52 14.26 89 0.6 15.6 <2 0.21 <0.2 <0.5 25 77.1 19 12,744 152106105 <0.1 1,796 <1 <2 8.25 19 0.1 1.3 <2 <0.5 <0.2 <0.5 <10 8.2 613,906 15 106106 <0.1 1,683 <1 <2 7.06 121 0.3 <0.1 <2 0.23 <0.2 <0.5 145.4 29 12,471 137 106100 0.10 2,773 1 <2 2.91 229 0.5 2.1 <2 0.14 <0.2<0.5 15 6.1 15 9,566 39 106149 <0.1 1,595 <1 3 6.29 68 0.3 16.4 <2 0.16<0.2 <0.5 11 14.0 17 12,253 93 1106150 0.20 5,566 2 5 3.57 244 0.7 3.2<2 0.16 <0.2 0.6 23 5.4 20 8,862 44 106151 0.10 2,536 1 <2 5.82 163 0.87.1 <2 0.31 <0.2 <0.5 19 65.9 28 12,019 258 106152 0.17 2,861 1 3 3.86197 0.3 2.3 <2 0.16 <0.2 <0.5 20 4.7 27 10,540 34 106153-4 0.20 3,008 4<2 0.39 578 0.7 1.9 4.5 0.09 <0.2 1.2 32 6.4 8 5,599 31 0.11 1,975 <21.18 320 0.4 1.3 0.07 <0.2 <0.5 18 4.4 7 4,954 27

For the data collected in Tables 8A-8C, for the +1.3 mm oversizedmatter, the materials were not able to be assayed as it was too coarseand heterogeneous. The amounts were estimated by grading by magnetic andvisual classification (on half the material) and found the following:81.7% copper color flakes (assumed to be pure copper for the massbalance); 10.6% magnetic flakes (assumed to be pure iron, although itprobably contains other metals as well); 6.7% non-magnetic metals (notused in mass balance); and 1.0% carbon-like material (not used in massbalance). It was further assumed there were no precious metals in theseoversized matter.

The data shows that the methods of the invention maintain the form ofthe metals and other elements, without introducing any contaminantsand/or other hazardous materials. This beneficially, preserves the valueof the metals and other elements.

As shown in Table 9, a gravity test mass balance is shown for theelements gold, palladium and platinum. This further demonstrates thatspecific metals and/or other elements of commercial interest can berecovered at high concentrations from the Char source according to theinvention.

TABLE 9 Grade Dist % Element Weight (grams) 19.2 Au 635.93 98.7% Pd53.28 69.9 Pt 0.22 54.3

Example 5

As confirmed in Example 1, the methods of the invention have safelyconverted hydrocarbon materials containing halogens without creatingPAHs. Exemplary e-waste sources include a typical desktop computermotherboard weighing approximately 1 pound. Of this total mass, about30% will be in the board itself. The board also contains about 50%fiberglass for strength. This leaves about 15% for the resin binders.The bromine content of a PWB may be as high as 18%. Thus the halogencontent may be around 2-3% by mass.

The methods of the invention are further evaluated to confirm processingof e-waste sources comprising up to 7%, 8%, 9%, 10% or more halogensprocessed according to the invention do not create PAHs, halogenateddibenzodioxins, halogenated dibenzofurans, biphenyls, and/or pyrenes.The confirmed tolerance level of the methods are from at least 7-10%halogens processed according to the invention without creating PAHs,halogenated dibenzodioxins, halogenated dibenzofurans, biphenyls, and/orpyrenes. Beneficially, the methods of the invention do not produce newmolecules and further eliminate those contained in the e-waste sourceinput itself.

Beneficially, as shown the methods of the invention are further able tovolatilize and thereby effectively remove mercury through its capture inthe scrubber system. As no mercury was detected in the Char residueand/or the gas produced according to the methods, the methods aredemonstrated to be safe and effective for processing mercury containinge-waste without the requirement for removal of any mercury components bymanual means. In a further assessment utilizing a sample of autoshredder residue, 50 ml of mercury was injected prior to the processing.After processing, no mercury was found in the char or in the gas,confirming complete removal by the scrubbers.

Example 6

Additional testing at a pilot facility was conducted as set forth inExamples 2 and 3, with the following modifications to the plantconditions for processing of ABS and Polystyrene feedstock as an e-wastesource, namely the plastics accompanying e-waste:

-   -   Plant operation with the lower burner only    -   Feedstock infeed in short intervals    -   Reactor conditions with temperatures of 600° C. at the reactor        top and 650° C. to 700° C. at the lower parts of the reactor.    -   Release of the gas from the gas dome to scrubber 1, no direct        connection from the reactor head to scrubber 4.    -   Steam generation via heat exchanger and injection of the steam        through special pipelines directly into the reactor head.    -   The Cracker-module for generated condensates was not in        operation, because the volume of these oils was too low for an        efficient operation.    -   The operation of the gas scrubbers was carried out without        recirculation.        -   Level control in scrubber 1 and 2 by manual adjustments of            the correct level.        -   Control of the oil water separator between the scrubbers and            the gas pipeline of the plant during operation.

Special conditions for the test operation:

-   -   The selected basic operating parameters were continuously        monitored and needed only miniscule adjustments. The Infeed        volume of the feedstock was increased during the second phase of        the test.    -   The feedstock input was continuous—in selected intervals. Due to        the high reactivity and fast gasification of the feedstock, a        pulsating increase in gas volume and pressure was monitored.        This effect had no negative impact for the test operation. An        increase of feedstock caused more gas generation and the slight        pressure increase in the range of a few mbar had no impact on        the test operation.    -   The water content in the reactor was slightly increased by steam        injection, which increased the gas generation due to the        chemical balance reactions.    -   The gas volume was constantly measured. The generated gas volume        during phases of increased feedstock supply was at 30 m3/h and        above, the average value was at ca. 15 m3/h.    -   The scrubber operated at normal stationary conditions. The        differential pressure was in the range like the differential        pressure in previous test runs.    -   No recirculation and injection of the generated oils from        scrubbers 1 and 2. The low amount of oil components was removed        from scrubbers 1 and 2 and collected.    -   The level control of the media during operation was adjusted        constantly to its range level. All generated media (i.e. liquids        contained in the scrubbers that also include relevant additives        such as NaOH) were removed after the test and measured for the        mass balance. As referred to herein for the media, the media are        defined as oil and water with additives for gas cleaning.    -   No special technical adjustments were necessary during the test        operation, the adjustments for this feedstock had been        implemented in accordance with the instructions of the customer        before the test run. No technical failures occurred. The plant        operated perfectly stably and its capability to process this        feedstock was proven.

TABLE 10 Summary test operations Plant operation volumes Input - total250 kg Average throughput 1. Phase/2. Phase 70/35 kg/h

The temperature and pressure measurements are shown in FIGS. 18-19(measured in degrees Celsius) where Temperature 1 is the middle part ofreactor; Temperature 2 is at the reactor head; and Temperature 3 is atthe gas dome (FIG. 18) and Pressure (mbar) compared to flow rate isshown (FIG. 19).

Evaluation of the measured values and data. The plant was operated witha temperature range in the reactor of 600° C. to 700° C. The pressure inthe reactor was on average >5 mbar. Significant pressure spikes were notrecorded despite the high reactivity and rapid gasification of thematerial and pressure spikes stayed below 10 mbar. The throughput changeof the feedstock is recorded in the measured data. The generated gasvolumes had significant spikes due to high reactivity of the material;which this effect could be equalized by a more constant infeed volume.The reactor head temperatures were at 600° C. These temperatures can beachieved also with a higher throughput as it will be regulated by theheat transfer capabilities of the Char.

Temperature control and the volume of scrubbed-out components arerelevant for the evaluation of the data from the gas scrubbing units.The temperature of scrubber 1 was regulated at ca. 79° C., scrubber 2 at60° C. and 3 at 30° C. Media (water or oil and chemicals) were added tocontrol the temperatures and filling level of the scrubbers. Thecondensates in scrubber 1 were long-chained hydrocarbons, which will bereinjected into the reactor. Water and aromatics were scrubbed out inscrubber 2. Process water without oil components were was scrubbed outin No 3. The oil components are aromatics, which can be reinjected intothe process.

Absorption process. An additional scrubber was used to detect mercuryand HBr. This scrubber was operated first with aqua regia to detectmercury and in a second phase with highly concentrated Sodium Hydroxide(NaOH). Neither Brominated salts nor Mercury could be detected.

Explanations to the test operation. The reactivity of the test materialwas unknown. The gas production was pulsating due to the high reactivityof the feedstock, which caused no problems during the test at the pilotplant. The test samples were delivered to the laboratory after the testrun for analysis. The analysis was done by using one representativesample for the Input and Char, three gas samples were analyzed.

Sampling, Analysis, Evaluations. The feedstock and the Char samples werecollected and analyzed. An additional analytical test for dioxins in thefeedstock and Char was ordered. The test samples were delivered to thelaboratory after the test run for analysis. The analysis was done byusing one representative sample and the conditions of differentfeedstock content could not be evaluated at this test.

Analysis data and M+E Balance. The results of the analysis are shown inTables 11-13.

TABLE 11 Mass balance Output Input Oil/ Input Steam Gas Oligomeres CharWater Mass [kg] 250 30 110 65 57 45*

TABLE 12 Analysis feedstock material Analysis parameter Value DimensionDry residue (TR) 99.2 Ma.-% HF-Digestion Iron 304   mg/kg Aluminum 417  mg/kg Copper 73   mg/kg Zinc 66.5 mg/kg Tin 40.5 mg/kg Cadmium <0.1mg/kg Chromium 10.4 mg/kg Nickel 17.2 mg/kg Lead 36.7 mg/kg Bromine<100*   mg/kg Heating value 22 970    kJ/kg Chlorine  0.04 Ma.-%Bromine <100*mg/kg: The laboratory accounted Bromine in the two digitrange, but could not quantify it exactly and chose a conservative valueof <100*mg/kg.

TABLE 13 Dioxin Analysis parameter Dimension BG Value PCDD/PCDF2,3,7,8-TetraCDD ng/kg TS <1 <1 1,2,3,7,8-PentaCDD ng/kg TS <1 <11,2,3,4,7,8-HexaCDD ng/kg TS <1 <1 1,2,3,6,7,8-HexaCDD ng/kg TS <1 <11,2,3,7,8,9-HexaCDD ng/kg TS <1 <1 1,2,3,4,6,7,8-HeptaCDD ng/kg TS *< 

<5 OctaCDD ng/kg TS *< 

<10 2,3,7,8-TetraCDF ng/kg TS < 

<1 1,2,3,7,8-PentaCDF ng/kg TS <1 <1 2,3,4,7,8-PentaCDF ng/kg TS <1 <11,2,3,4,7,8-HexaCDF ng/kg TS <1 <1

1,2,3,7,8,9-HexaCDF ng/kg TS <1 <1 2,3,4,6,7,8-HexaCDF ng/kg TS <1 <11,2,3,4,6,7,8-HeptaCDF ng/kg TS <3 <3 1,2,3,4,7,8,9-HeptaCDF ng/kg TS <3<3 OctaCDF ng/kg TS <1 

<10 PBDD/PBDF 2,3,7,8-TetraBDD ng/kg TS <1 

<10 1,2,3,7,8-PentaBDD ng/kg TS <1 

<10 1,2,3,4,7,8-HexaBDD ng/kg TS <5 

<50 1,2,3,6,7,8-HexaBDD ng/kg TS <5 

<50 1,2,3,7,8,9-HexaBDD ng/kg TS <5 

<50 2,3,7,8-TetraBDF ng/kg TS

<10 1,2,3,7,8-PentaCDF ng/kg TS <1 

<10 2,3,4,7,8-PentaCDF ng/kg TS <1 <10

indicates data missing or illegible when filed

The results above analyzed a representative sample from severalcollected samples. The e-plastics evaluated contain flame retardants inthe feedstock which contain Bromine, which was analyzed with <100 mg/kg.The analysis of the dioxins in the feedstock are shown in table 5 and nodioxins are present in the feedstock.

The flame and/or fire retardants in the PWB feedstock are known tocontain Bromine, which was analyzed at 2% in the feedstock. The analysisof the dioxins in the feedstock showed elevated levels of dioxins in thefeedstock. Target of the test was to avoid creating new dioxins andreduce existing dioxins by cracking.

Analysis of the Product Gas. The results of the analysis are shown inTable 14.

TABLE 14 Product Gas (in Volume percentage) Main Components Gas Gas[Vol-%] 7_1_31 7_1_33 H₂ 25.3 21.4 O₂ 0.68 0.39 N₂ 2.4 1.6 CH₄ 38.0 34.5CO₂ 8.6 13.0 CO 14.8 13.1 Ethane 2.3 3.0 Ethene 5.0 5.1 Propane <0.050.24 Propene 0.87 1.7 i-Butane <0.01 <0.01 n-Butane 0.01 0.01

The samples of the generated gas were collected in Phase 1 and Phase 2(12.10, 15.10, 17.10). The analysis results reflect homogeneousoperating conditions. The gas analysis shows a relative high Methanecontent and low paraffin content. The ratio of CO and CO2 ischaracteristic for this temperature profile. Oxygen and Nitrogen are notcomponents of the original gas compositions, but intruders into the gassample during the transport of the glass vessels.

The molecular structure of the feedstock is characterized by an highPolystyrene content. Larger volumes of benzene and Methane are theresult of this feedstock composition. The aromatic components of the gasvapor will not be totally cracked without the cracking reactor and willgenerate a liquid fraction with low viscosity. The low amount ofgenerated oily components can be pumped at average temperatures and canbe converted with the cracking reactor.

Analysis of Char-Metal mixture. The results of the analysis are shown inTables 15-16.

TABLE 15 Char-Metal mixture Analysis parameter Value Dimension DryResidue (TR) 94.6 Ma.-% Carbon, raw 63 Ma.-% Heating value, raw 22.390kJ/kg Ash content, raw 28.6 Ma.-% Aluminum 9.860 mg/kg Copper 9.050mg/kg

TABLE 16 Dioxins Analysis parameter Dimension BG Value PCDD/PCDF2,3,7,8-TetraCDD ng/kg TS 1 <1 1,2,3,7,8-PentaCDD ng/kg TS 1 <11,2,3,4,7,8-HexaCDD ng/kg TS 1 <1 1,2,3,6,7,8-HexaCDD ng/kg TS 1 <11,2,3,7,8,9-HexaCDD ng/kg TS 1 <1 1,2,3,4,6,7,8-HeptaCDD ng/kg TS 5 <5OctaCDD ng/kg TS 10 *<17 2,3,7,8-TetraCDF ng/kg TS 1 <11,2,3,7,8-PentaCDF ng/kg TS 1 <1 2,3,4,7,8-PentaCDF ng/kg TS 1 <11,2,3,4,7,8-HexaCDF ng/kg TS 1 <1 1,2,3,6,7,8-HexaCDF ng/kg TS 1 <11,2,3,7,8,9-HexaCDF ng/kg TS 1 <1 2,3,4,6,7,8-HexaCDF ng/kg TS 1 <11,2,3,4,6,7,8-HeptaCDF ng/kg TS 3 <3 1,2,3,4,7,8,9-HeptaCDF ng/kg TS 3<3 OctaCDF ng/kg TS 10 <10 Sum PCDD/PCDF (WHO TE ng TE/kg (n.b.*) 2005)TS PBDD/PBDF 2,3,7,8-TetraBDD ng/kg TS <10 <10 1,2,3,7,8-PentaBDD ng/kgTS <10 <10 1,2,3,4,7,8-HexaBDD ng/kg TS <50 <50 1,2,3,6,7,8-HexaBDDng/kg TS <50 <50 1,2,3,7,8,9-HexaBDD ng/kg TS <50 *<180 2,3,7,8-TetraBDFng/kg TS <10 *<10 1,2,3,7,8-PentaCDF ng/kg TS <10 <10 2,3,4,7,8-PentaCDFng/kg TS <10 <10

As shown in Table 15, the Char was analyzed for metal particles. Inaddition to the analyzed make-up of the metals in the remaining Char,approximately a 25 kg sample of the clean Char was sent for furtherassessment by separation and assay. The Char was separated by size.FIGS. 10-15 show photographs of separated materials in phases ofseparation according to optional embodiments of the invention from cleanChar including: Oversized copper materials (1.3+ mm) (FIG. 10), Smallersized copper and precious metal materials (FIG. 11), additional finersized copper and precious metal materials (FIG. 12), <300 um sizedcopper and precious metal materials (FIG. 13), additional finer sizedcopper and precious metal materials (FIG. 14), and primarily fine carbonmaterial (FIG. 15). The char was first separated by passing through atrammel, then two shaking tables to separate materials +1.3 mm oversizeand +600 μm. Two subsequent shaking tables collected approximately 600μm and smaller sizes. Finally, rotary separation was used to collect thesmallest parts of the char and unusable fines.

As shown in Table 16, the Char was further analyzed for any remainingdioxins. The results shown confirm the destruction of the flameretardants without generation of dioxins as a result of the methods ofprocessing according to embodiments of the invention as shown by dioxincontent in the Char being non-detectable.

Overall results. The plant operation with the delivered feedstock wassuccessful. The technical design of the pilot plant demonstrated thedesired processing of the e-plastics feedstock. A gas for multipleapplications has been generated and a Char-metal mixture suitable forfurther processing was obtained. Further benefits include theconfirmation that no dioxins generated and existing dioxins cracked,confirming reduction to practice of not creating any toxic materialsresulting from the brominated flame and/or fire retardants in thee-plastics. Accordingly, the pilot plant demonstrated a stableperformance with neither the composition of the plastics nor the metalshaving any negative impact on the process.

The results of the evaluation confirmed the methods of the inventionmeet the requirements for this specific feedstock consisting mostly ofABS and Polystyrene. The operation of the plant was verified for thismaterial type in regard to its composition, melting specifications andexpected fast gasification performance. The product specifications andthe gas composition were as follows: (1) The gas has a suitablecomposition with high methane, hydrogen and carbon monoxide and low CO2content for further usage; (2) Hydrogen bromide has been neutralized inthe gas scrubbers with sodium hydroxide; (3) The gas scrubbingefficiency was verified with an absorber after the scrubbers; (4) Thedestruction of the flame retardants without generation of dioxins wasproven: the dioxin content in the Char was not detectable; and (5) Themetal particles and the remaining Char were collected after the process(mechanically).

1. A method for converting an electric and/or electronic waste source toa Clean Fuel Gas and Char source comprising: inputting an electric andelectronic waste source into a thermolysis system; wherein thethermolysis system comprises at least two reactors and an oil/tarcracker; and undergoing a depolymerization and a cracking reaction ofhydrocarbons in the waste source; destroying and/or removing toxiccompounds present in the waste sources; and generating the Clean FuelGas source and Char source, wherein the Clean Fuel Gas source is used topower a system or application; wherein the Char source containsrecoverable metals; and wherein the Clean Fuel Gas source and Charsource are substantially-free of halogenated organic compounds.
 2. Themethod of claim 1, wherein the electric and electronic waste source isan e-waste source selected from the group consisting of printed wiringboards, thermoplastic materials, flat panel displays, printer cartridgesand/or cassettes, and combinations thereof.
 3. The method of claim 1,wherein the thermolysis system comprises at least one reactor with aprocess temperature of about 300° C.-800° C. for the waste source toundergo at least partial gasification.
 4. The method of claim 1, whereinthe thermolysis system is provided with indirect heat that is free ofoxygen.
 5. The method of claim 1, wherein the thermolysis system has apressure range from about 10 to about 100 millibar.
 6. The method ofclaim 1, wherein the waste source is substantially uniform in sizehaving an average diameter of less than 1 inch and the method furthercomprises an initial step of shredding or grinding the waste source thatis larger than 1 inch in diameter.
 7. The method of claim 1, wherein thetoxic compounds destroyed and/or removed comprise aromatics andpolycyclic aromatic hydrocarbons, halogenated dibenzodioxins,halogenated dibenzofurans, biphenyls, pyrenes, cadmium, lead, antimony,arsenic, beryllium, chlorofluorocarbons, mercury, nickel and otherorganic compounds present in the waste source, and wherein the CleanFuel Gas and Char source generated contain less than about 10 ppb of thehalogenated organic compounds.
 8. The method of claim 1, wherein thetoxic compounds destroyed comprise toxic halogenated organic compounds.9. The method of claim 81, wherein the waste source is an e-waste sourceand comprises up to 10 wt.-% of halogens or halogenated compounds andthe method does not generate polycyclic aromatic hydrocarbons,halogenated dibenzodioxins, halogenated dibenzofurans, biphenyls, and/orpyrenes.
 10. The method of claim 1, wherein the method does not generateany toxic halogenated organic compounds in the process of converting thewaste sources to the Char source and Clean Fuel Gas sources.
 11. Themethod of claim 1, wherein the Char source is in the form of a metallicstate that is fine, flake and/or chip containing valuable electronicmetals, rare earth metals, precious metals, glass reinforcement and/orother materials, and wherein the method further comprises an additionalstep of removing the valuable electronic metals, rare earth metals,precious metals, glass reinforcement or a combination thereof from theChar source.
 12. The method of claim 1, wherein the method furthercomprises separating oil soluble substances from a gas/vapor mixture inthe Clean Fuel Gas source following the thermolytic conversion ofhydrocarbons in the waste source.
 13. The method of claim 12, whereinthe separation is done in a gas scrubber wherein the gas is scrubbed andthe vapor undergo fractionated condensation.
 14. The method of claim 1,wherein at least a portion of the Clean Fuel Gas source used to generateheat.
 15. The method of claim 14, wherein the Clean Fuel Gas sourcegenerates from about 3,000 to 19,000 BTUs per pound of the waste source,and wherein the Clean Fuel Gas source and Char source do not includetars and/or oils.
 16. A method for converting e-waste sources to a CleanFuel Gas source and Char source comprising: shredding or grinding ane-waste source to provide a substantially uniform e-waste source havingan average diameter of less than 1 inch, inputting the uniform e-wastesource into a thermolysis system comprising at least two reactors and anoil/tar cracker with a process temperature of about 300° C.-800° C. anda pressure range of from about 10 to about 100 millibar, wherein thethermolysis system is provided indirect heat that is free of oxygen;undergoing a depolymerization and a cracking of hydrocarbons in thee-waste source; destroying and/or removing toxic compounds present inthe e-waste source; generating a Char, wherein the Char source is in afine metallic state that is free of halogenated organic compounds andthe Char source comprises valuable electronic metals, rare earth metals,precious metals, glass reinforcement, or a combination thereof;separating the metals, glass reinforcement, a combination thereof fromthe Char source; generating a Clean Fuel Gas source from the pyrolyticconversion of hydrocarbons in the e-waste source, wherein the Clean FuelGas source is free of halogenated organic compounds; and wherein theClean Fuel Gas source and Char source do not include tars and/or oils.17. The method of claim 16, wherein the e-waste source is selected fromthe group consisting of printed wiring boards, thermoplastic materials,flat panel displays, printer cartridges and/or cassettes, andcombinations thereof, and comprises halogens or halogenated compoundsand the method does not generate polycyclic aromatic hydrocarbons,halogenated dibenzodioxins, halogenated dibenzofurans, biphenyls, and/orpyrenes.
 18. The method of claim 16, wherein the toxic compoundscomprise aromatics and polycyclic aromatic hydrocarbons, halogenateddibenzodioxins, halogenated dibenzofurans, biphenyls, pyrenes, cadmium,lead, antimony, arsenic, beryllium, chlorofluorocarbons, mercury,nickel, or a combination thereof present in the e-waste source, andwherein the method does not generate any toxic halogenated organiccompounds in the process of converting the e-waste sources to the Charsource and Clean Fuel Gas source.
 19. The method of claim 16, whereinthe method further comprises separating oil-soluble substances from agas/vapor mixture in the Clean Fuel Gas source following the pyrolyticconversion of hydrocarbons in the e-waste source, and wherein the methodfurther comprises scrubbing the gas/vapor mixture, wherein the gas isscrubbed and the vapor components undergo fractionated condensation. 20.A Clean Fuel Gas and Char source produced by the process of claim 1.